TW521280B - Method of producing transparent conductive film-laminated substrate and method of producing color filter - Google Patents

Abstract

The present invention provides a method of producing transparent conductive film-laminated substrate, which comprises the steps of: (1) sputtering sintered body of indium-tin oxide as an target in an atmosphere of inert gas or of inert gas-oxygen mixed gas by using DC or DC+RF power supply to form an ITO film on a substrate, and (2) sputtering at least one target selected from the group comprising sintered bodies of indium-tin oxide and indium oxide in an inert gas atmosphere by using DC, RF or DC+RF power supply to form an ITO film and/or an indium oxide film on the ITO film obtained in the step (1). The invention provides a color filter with excellent conductivity and transparency by processing a substrate coated by a light-shielding film, a color resist film or the like by means of the above ITO film forming steps.

Description

521280 Α7 I --------- 5. Description of the invention (1) [Technical Field] The present invention relates to a method for manufacturing a transparent conductive film laminated substrate and a color filter. [Known Technology] TFT displays, which have become mainstream in displays for notebook computers and desktop computers, constitute a state where light from a light source passes through TFTs, liquid crystal molecules, and color filters to form an image on a substrate. As a method for producing a color phosphor film, there are known methods described in, for example, Japanese Patent Application Laid-Open No. 63-197903 and Japanese Patent Application Laid-Open No. 6-28932. Japanese Patent Application Laid-Open No. 63-197903 discloses that a glass substrate formed with a light-shielding film and a color photoresist film is heated to 18 (rc, and a target made of a tin-indium oxide sintered body is sputtered. Or a method of forming an ITO conductive film on a glass substrate having a light-shielding film and a color filter film formed by subjecting an indium tin alloy target to reactive sputtering in an argon atmosphere gas containing oxygen to a target. However, the ιτο v electrical film obtained by the method disclosed in JP-A-63-197903 is composed of a single layer, which has the disadvantage of low conductivity (ie, large resistivity). If it is necessary to improve the conductivity of IT0 If the conductivity of the film is necessary, it is necessary to make the film thickness of the conductive film thick. However, once the thickness of the ITO conductive film is made thick, the transparency of the conductive film cannot be avoided. Therefore, in this way, The ITO conductive film obtained by the method cannot satisfy both high conductivity and transparency. Japanese Patent Laid-Open No. 6-28932 discloses a method for forming an ITO conductive film on the surface of an organic resin formed on a color photoresist film. This side The standard of this paper is applicable to China National Standard (CNS) A4 specification (2) 0 X 297 public love. {Please read the notes on the back before filling this page.)

-------- ^ --------- -4- 521280 A7 B7 V. Description of the invention (-------------- install --- (please first Read the notes on the reverse side and fill in this page) (a) On the surface of the organic resin, use a tin-indium oxide sintered body as the target, and 锿Step of coating a crystal nucleation layer (layer) with a thickness of 3 to 3 Onm in a direct current magnetron (magnetron) sputtering method in an ambient gas, (b) decompressing the crystal nucleation layer to an ambient gas Step of growing the crystal nucleus by annealing at a temperature not lower than the aforementioned organic resin of 10 (rc), and on the crystal nucleation layer, an argon gas and an oxygen gas containing 3% by volume of argon or oxygen Step of coating a low-resistance layer (second layer) with a DC magnetron sputtering method in an ambient gas of a mixed gas. There are two methods for reducing the resistivity of an ITO conductive film. The first method is to increase the mobility of the carrier (free electron), and the second method is to increase the density of the carrier (free electron). Japanese Patent Application Laid-Open No. 63-11979 The method described in the bulletin is to increase the density of the carrier, and as a result, it is necessary to reduce the resistivity of the 170 conductive film, that is, to increase the conductivity. However, according to this method, although the carrier mobility will increase However, the effect of improving the conductivity is not accompanied by the decrease in the density of the Φ body. The method disclosed in Japanese Patent Application Laid-Open No. 6-28932 is not practical because it requires a special treatment called annealing. As a method for forming an ITO conductive film, for example, a method described in Japanese Patent Application Laid-Open No. 2-189816 is known. The above-mentioned publication discloses that a method including a depressurized inert gas or In an ambient gas of mixed gas, a target of indium-tin oxide sintered body is used, and a substrate maintained at 200 ° C is magnetized by a magnetron. Centimeters) 521280

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

A step of forming a first layer of ITO film by an official sputtering method; a step of heating the substrate to 300 ° C or more under reduced pressure; in an ambient gas containing a mixed gas of a reduced pressure inert gas and oxygen, A step of forming a second layer of ITO film on the first layer of the substrate heated above 300 ° C by a magnetron sputtering method using the aforementioned target; placing the substrate in a reduced-pressure ambient gas A step of returning the ambient gas to atmospheric pressure after cooling below 250 ° C. A method for forming an ITQ conductive film composed of two layers on a substrate. The method described in Japanese Patent Application Laid-Open No. 6-28932 also increases the density of the carrier. As a result, it is necessary to reduce the resistivity of the IT0 conductive film, that is, to increase the conductivity. However, although the mobility of the carrier can be increased according to this method, the effect of improving the conductivity is not sufficient because the density of the carrier does not increase. In addition, the above method involves exposing the substrate to a high temperature of 30 ° C or higher, so that there is a disadvantage that the usable substrate is limited. In addition, the above method is necessary to reduce the pressure from 20000 under reduced pressure. c is heated below 300 ° c to a high temperature above 300 ° c, and cooled from a temperature above 30 ° c to below 25 ° t, so it takes a long time to heat and cool down. The above method includes a reduced pressure environment The substrate is cooled to 250 in the gas. (The following steps are to return to atmospheric pressure. This step is to return the substrate heated to the above temperature to atmospheric pressure, and then heat it to 3001 or higher. The substrate is oxidized by contact with oxygen, and as a result, it is necessary to prevent the substrate from being deteriorated. Therefore, the method disclosed in Japanese Patent Application Laid-Open No. 6-28932 is not practical because of the complicated operation of heating and cooling the substrate to a high temperature. τ: -------- tr --------- line (please read the precautions on the back before filling this page)

This paper is suitable for the national standard iMCNS) A4 specification (21 × x tear) 521280 A7 V. Description of the invention (4) [Disclosure of the invention] One of the objectives of the present invention is to provide a laminate with high conductivity and excellent transparency. Manufacturing method of substrate of conductive film. Another object of the present invention is to provide a method for producing a light sheet having high electrical conductivity and excellent transparency. The present inventors have repeatedly conducted various studies in order to achieve the above-mentioned object. As a result, it can finally be known that when the ITO film is formed on the substrate, at least two ITO films must be formed on the substrate, and the power used to form each of the ITO films must use a specific power source and use a specific sputtering method. Sputtering in a plating gas environment can increase the carrier concentration of the ITO film, so a substrate with a conductive film laminated with high conductivity and excellent transparency can be obtained. It is also known that the above-mentioned conductive film is laminated on a transparent substrate on which a light-shielding film and a color photoresist film are formed, whereby a color filter can be obtained in which a conductive film having high conductivity and excellent transparency is laminated. Furthermore, it has been found that the desired conductive film laminated substrate and color filter can be obtained even if a part of the above-mentioned many 1-but films is replaced with an indium oxide film. The present invention has been completed based on these findings. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics The present invention provides a method for manufacturing a transparent conductive film laminated substrate. This method has (1) using a DC (direct current) power supply or a DC + RF (high frequency) power supply, and sputtering an indium-tin oxide sintered body in an inert gas or an ambient gas of a mixed gas of inactive gas and oxygen. A step of forming an IT0 film with a target; and (2) at least one target selected from the group consisting of an indium-tin oxide sintered body and an indium oxide sintered body, using a DC power source, an RF power source, or a DC + RF power source Applicable to China National Standard (CNS) A4 specification (210 X 297 public love) V. Description of the invention (5) Sputtering in an inert gas ambient gas on the 1-but film formed in (1) above A step of forming an ITO film and / or an indium oxide film. The invention provides a method for manufacturing a transparent conductive film laminated substrate. This method has the following features: (1) using a DC power source or a DC + RF power source to sputter the target of indium-tin oxide sintered in an inert gas or a mixed gas of inactive gas and oxygen ^ environment gas to form a first on a substrate; Step of 1 layer of 1 film; (2) Using a DC power supply or a DC + RF power supply to sputter the above target in a mixed gas of inert gas and oxygen to form a second layer of ITO on the first layer Film step; and (3) using £) (: power supply or DC + RF power supply to sputtering the above target in an inert gas or a mixed gas of inert gas and oxygen gas to form a first layer on the second layer 3 steps of IT0 film. The present invention provides a transparent conductive film laminated substrate manufactured according to the above-mentioned various methods. The present invention provides a method for manufacturing a filter, which sequentially forms a light-shielding film and colored light on a transparent substrate. A method for manufacturing a resist film and a filter with at least two conductive films, wherein the conductive film forming step includes (1) using 〇 ([: power supply or DC + RF power supply, inert gas or inert gas and oxygen Mixed gas A step of sputtering an indium-tin oxide sintered body in an ambient gas to form an ITO film; and (2) at least _ Yuzi selected from the group consisting of an indium-tin oxide sintered body and an indium oxide sintered body A step of forming an IT0 film and / or an indium oxide film on the IT0 film formed by the above (1) by using a DC power supply, an RF power supply, or a DC + RF power supply to extinguish plating in an inert gas ambient gas; The present invention provides a method for manufacturing an optical filter, which is printed on a transparent substrate 521280 Α7 Β7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (sequentially forming a light-shielding film, a color photoresist film, and at least three layers A method for manufacturing a conductive film filter, wherein the conductive film forming step includes (1) using a DC power source or a DC + RF power source to indium-tin oxide sintered target in an inert gas or a mixed gas environment of inactive gas and oxygen A step of forming a first layer of ITO film on a substrate by sputtering in a gas; (2) using a DC power source or a DC + RF power source to perform sputtering on the target in a mixed gas environment gas of inert gas and oxygen, and On the 1st A step of forming a second layer of ITO film on the layer; and (3) using a DC power source or a DC + RF power source to perform sputtering on the target in an inert gas or a mixed gas of inert gas and oxygen, and apply The step of forming a third layer of ITO film on the layer. The present invention is to provide a filter manufactured according to the above-mentioned various methods [inventive mode of the invention] Manufacturing of transparent conductive film laminated substrate: The transparent conductive film laminated substrate of the present invention is Manufactured by a method of forming at least two ITO films or at least one ITO film and at least one oxide film on a substrate. The ITO film formed on the substrate may be two, three, four, or five layers. Or these and above. In addition, the indium oxide film may be one, two or more. Each of these ITO films is formed on a substrate by a conventional method. The present invention must use at least one of the two or more layers of the butadiene film formed by (1) using a DC power supply or a DC + RF power supply between an inactive gas or an inactive gas and oxygen. In an ambient gas of a mixed gas, an IT0 film is formed by sputtering a target of an indium-tin oxide sintered body; and in this way, I --- I--order -------- (Please read the notes on the back before filling this page)

521280 A7 _____B7__ 5. Description of the invention (7) (Please read the precautions on the back before filling out this page) on the ITO film, and (2) will be used from the indium-tin oxide sintered body and the dried indium oxide sintered body. A DC power source, an RF power source, or a DC + RF power source is formed by sputtering in an inert gas ambient gas to form an ITO film and / or an indium oxide film. The conductor density in the conductive film of the conductive film formed through the above steps (1) and (2) will become higher, and the mobility of the carrier will hardly decrease, and under some sputtering conditions, the carrier density in the conductive film It will become high, and the mobility of the carrier will also become large, so the conductive film has a high conductivity. The transparent conductive film laminated substrate of the present invention can be produced in more detail, for example, by the following methods A to C. Method A: (1) Use a DC power source or a DC + RF power source to form an ITO film by sputtering a target of an indium-tin oxide sintered body in an inert gas or a mixed gas of an inactive gas and oxygen. Step; and (2) applying at least one target selected from the group consisting of indium-tin oxide sintered body and indium oxide sintered body in a non-reactive gas ambient gas using a DC power source, an RF power source, or a DC + RF power source. A step of pre-sputtering to form an ITO film and / or an indium oxide film on the IT0 film formed in (1) above. The substrates printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs can use publicly known substrates. For example, glass substrates, glass bad oxygen resin substrates, ceramic substrates, oxide substrates, stone substrates, and aluminum nitride substrates can be used. , Metal substrate, IMS substrate, metal core substrate, hollow substrate, resin substrate, etc. Examples of the resin material of the resin substrate include polycarbonate, polyether, wind, polyimide, acrylic resin, and cyclic polybrominated hydrocarbons (for example, Nippon Chicai (Co., Ltd.)). Polyallylic acid ester, polyethylene naphthalate (PEN), polyethylene terephthalate (pET), etc. -10- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 521280 A7 printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (A glass substrate is preferred among these substrates. Glass The substrate can be widely used, for example, a glass substrate for a light-shielding sheet, and specifically, such as a glass substrate. The size and thickness of the substrate can be appropriately selected according to the purpose of use of the transparent conductive film laminated substrate. A method used The target is an indium-tin oxide sintered body. This sintered body is well known. For example, finely powdered tin oxide and finely powdered indium oxide can be sufficiently mixed to form a predetermined shape under pressure. Those fired at a high temperature of about 1500 ° C. The content of tin oxide in the sintered body is not limited, but is generally about 3 to about 30% by weight, and preferably about 5 to about 15% by weight. In method A First, a sintered body of indium-tin oxide is used as a target, and sputtering is performed on the substrate to form a first layer of a thin film on the substrate (hereinafter, this step is referred to as a "first step"). This first The sputtering conditions in the steps are shown below. The power source is set to DC power or DC + RF power. The power source is preferably DC power. The conditions for applying power vary depending on the size of the target, so it cannot be generalized, but if it is set to 5 The size of the Yingye X 15 inch is as follows. When the power is DC power, it is generally about 0.1 to 1KW, preferably about 0.3 to 0.6KW. For DC + RF power, the power of the DC power Generally about 0.1 to about 1 KW ', preferably about 0.2 to about 0.6 KW, and the power of the RF power supply is generally about 0.1 to about 3 KW, preferably about 0.2 to about 0.6 KW. The DC / RF power ratio is in the range of about 0.1 to about 10 It can be adjusted appropriately. In the case of using RF power, frequency • 11-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Μ -------- ^ ----- ---- Line (Please read the precautions on the back before filling this page) 521280 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (9) The rate is usually about 6.78 ~ 27.12MHz, preferably About 13.56MΗζ. Although the temperature of the substrate varies depending on the type of substrate, it is used for example glass-based In general, the temperature is usually close to 300 ° C at room temperature, preferably about 140 to 250 ° C. The sputtering gas is an inert gas or a mixed gas of inert gas and oxygen, preferably an inert gas and A mixed gas of oxygen. Known inert gas can be widely used as the inert gas. Typical examples include gases such as argon. Gas pressure (sputtering pressure) is usually about 0.1 to about 1P, and preferably about 0.2 to 0.8 Pa. When a mixed gas of inert gas and oxygen is used in the first step, the oxygen content of the mixed gas is about 1% by volume or less, and preferably about 0.6% by volume or less. In the first step, the film thickness of the ITO film as the first layer on the substrate is usually about 5 to about 100 nm, preferably about 10 to about 70 nm, and most preferably about 15 to about 50 nm. In method A, Next, an indium-tin oxide sintered body was used as a target, and this was sputtered on the first layer formed on the substrate and a second layer of ITO film was formed on the first layer (hereinafter, this step is referred to as the "second step" "). The sputtering conditions in this second step are as follows. The type of power supply is DC power, RF power, or DC + RF power. The power source is preferably an RF power source. When the applied power is a DC power source, it is generally about 0.00 to about 1 KW, and preferably about 0.3 to about 0.6 KW. The power of the RF power supply is generally about 0 ~~ 3KW, preferably about 1 -12- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public) {Please read the precautions on the back before filling this Page) • -Ik Order --------- 521280 A7 B7 10 V. Description of the invention (~ about 1.8KW. If DC + RF power supply, the power of DC power supply is about 〇1 ~ about 1KW, the best About 0.2 ~ about 0.6KW, the power of RF power is generally about 0.1 ~ about 3KW, preferably about 0.2 ~ about 0.6KW. DC // RF power ratio is appropriately adjusted in the range of about 0.1 ~ about 10. That is, when using an RF power source, the frequency is usually about 6.78 to about 27 · 12 Μ 最好 ζ, preferably about 13.56 MHz. The temperature of the substrate forming the first layer is usually near room temperature to less than 300 ° C. It is preferably about 140 to about 250 ° C. The sputtering gas is an inert gas. Known inert gas can be widely used as the inert gas, and typical examples include gases such as argon. The gas pressure is usually about 0.1 to about 1P is preferably about 0.2 to 0.8 Pa. The thickness of the IT0 film as the second layer formed on the first layer in the second step is usually about 5 to about 100 nm, About 10 to 70 nm, preferably about 30 to 70 nm. In method A, the temperature of the substrate is maintained at about 14 to about 25 ° C. and the keying is performed twice, so that A 1-layer film composed of two layers is formed on the substrate. In this case, 'the substrate temperature is very low, so even if the ambient gas around the substrate is immediately returned to atmospheric pressure, there is no risk of the substrate being deteriorated. It can be completed in a short time in minutes. The following aspects are included in method A. (A— 1) Including: (1) Using a DC power source or a DC + RF power source, dry the indium-tin oxide sintered body in an inert gas. Or inert gas and mixed gas of oxygen and ambient gas to form ITO film on the substrate, and, -13- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ^- ------- ^ --------- line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 521280 A7 ____B7____ V. Invention Description (U ) (Please read the notes on the back before filling this page) (2) Use DC power, RF power DC + RF power supply, at least one dry element selected from the group consisting of indium-tin oxide sintered body and indium oxide sintered body, is subjected to base plating in an inert gas ambient gas and formed in the above (1) The manufacturing method of the transparent conductive film laminated substrate in the step of forming the ΓΓΟ film and / or the indium oxide film on the ITO film. (A-2), The manufacturing method of the transparent conductive film laminated substrate as described in (A-1), is The power of step (1) is set to DC power and the power of step (2) is set to RF power. (A-3), the manufacturing method of the transparent conductive film laminated substrate as described in (A-2), is performed by sputtering in step (1) in a mixed gas environment gas of inert gas and oxygen, and ( 2) The sputtering of the step is performed in an inert gas ambient gas. (A-4) The method for manufacturing a transparent conductive film laminated substrate as described in (A-3), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is 1% by volume or less. (A-5) The method for manufacturing a transparent conductive film laminated substrate as described in (A-4), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is 0.6% by volume or less. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (A-6) ′ The manufacturing method of the transparent conductive film laminated substrate as described in (A-1) is to set the power supply in step (1) to! ) ^ Power, set the power in step (2) to DC power. (A-7) 'The manufacturing method of the transparent conductive film laminated substrate as described in (A-6)' is performed by sputtering in step (1) in an inert gas and oxygen mixed gas ambient gas' and ( 2) Sputtering in a step in an inert gas environment -14- This paper size applies to China National Standard (CNS) A4 (210 X 297 male H)

521280 V. Description of the invention (12) Performed in gas. (A-8) The method for producing a transparent conductive film laminated substrate according to (A-7), wherein the oxygen gas content in the mixed gas of the inert gas and oxygen in step (1) is 1% by volume or less. (A-9) The method for manufacturing a transparent conductive film laminated substrate as described in (A-7), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is equal to or less than 0.6% by volume . (Α — 1〇) 'The manufacturing method of the transparent conductive film laminated substrate as described in (a — 1), wherein the power supply in step (1) is set to DC + RF power, and the power supply in step (2) is set to RF power supply. (Α — Π), the manufacturing method of the transparent conductive film laminated substrate as described in (Aug. 10), the sputtering in step (1) is performed in an inert gas ambient gas, and (A-12), such as ( The manufacturing method of the transparent conductive film laminated substrate according to A-10) is performed by sputtering in the step (1) in an inert gas and oxygen mixed gas ambient gas. (A-13) The method for manufacturing a transparent conductive film laminated substrate as described in (A-12), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is below 0.6% by volume . (A-14) The method for manufacturing a transparent conductive film laminated substrate as described in (A-13), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is 0.4% by volume or less. (A-15), The manufacturing method of the transparent conductive film laminated substrate as described in (A-14), which is -15 in the mixed gas of inert gas and oxygen in step (1). This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) --------- — — — — 1111111 ^ · 111111! (Please read the precautions on the back before filling out this page) Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperatives 521280 A7 ---------- B7____ 5. Description of the invention (13) The oxygen content is below 0.2% by volume. (A-16) The method for manufacturing a transparent conductive film laminated substrate as described in (A-1), where the power supply in step (1) is a DC power supply, and the power supply in step (2) is a DC + RF power supply . (A-17) The method for manufacturing a transparent conductive film laminated substrate as described in (A-16) is carried out by sputtering in step (1) in an inert gas and oxygen mixed gas ambient gas. (A-18) The method for manufacturing a transparent conductive film laminated substrate as described in (A-17), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is 1% by volume or less. (A-19) The method for manufacturing a transparent conductive film laminated substrate as described in (A-18), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is 0.6% by volume or less. Method B: Method B includes: (1) using a DC power source or a DC + RF power source to sputter the target of the indium-tin oxide sintered body in an inert gas or a mixed gas of an inactive gas and an oxygen gas to the substrate and sputter the substrate; Step of forming the first and the first layer of IT0 film; (2) Use a DC power supply or a DC + RF power supply to sputter the target on the dish in a mixed gas of inactive β gas and oxygen and place it on the j layer. A step of forming a second layer of ITO film; and (3) using a DC power source or a DC + RF power source to sputter the above target in an inert gas or a mixed gas environment gas of inert gas and oxygen on the second layer A step of forming a third layer of ITO film. This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love) (Please read the precautions on the back before filling out this page) 0 ΊδΊ · 1111111. Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-16- 521280 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (14 The substrate and target used in this method are the same as Method A. In Method B, first, an indium-tin oxide sintered body is used as the target And sputter plating on the substrate to form a first layer of 1 but film on the substrate (this step is hereinafter referred to as "the first step"). The conditions of the first step to remove the plating are shown below. Power supply Set to DC power supply or DC + RF power supply. The power supply is preferably a DC power supply. The conditions for applying power vary depending on the size of the target, so it cannot be generalized, but if the target is set to 5 inches x 15 inches, such as It is shown below. When the DC power is applied, it is usually about 0 ~ 1 ~ 1KW, preferably about 0.3 ~ 0.6KW. For DC + RF power, the power of DC power is generally about 0 ~ 1KW, most Good about 〇2 ~ 〇6KW, the power of RF power is generally about 0.1 ~ 3KW, preferably about 0.2 ~ 0.6KW. DC / RF power ratio can be adjusted appropriately within the range of about 0-1 ~ 10. Use In the case of an RF power supply, the frequency is usually about 6.78 to about 27 · 12 MHz, preferably about 13.56 MHz. Although the temperature of the substrate varies depending on the type of the substrate, when a glass substrate is used, for example, it is usually near room temperature. Over 300c, preferably about 140 ~ 250 ° C. The base plating gas is an inactive gas or a mixed gas of inactive gas and oxygen. The inert gas can be widely used as a known inert gas, and its representative Examples include gas such as argon. The gas pressure (sputtering pressure) is usually about 0.1 to about 1 P, preferably about 0.2 to 0.8 Pa. 〇-17- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------ II --- I- · IIIIIII Order! 111! _-^ (Please read the notes on the back before filling out this page) 521280 A7 B7 V. Description of the invention (15) In the case of using a mixed gas of inert gas and oxygen in the first step, in the case of a DC power supply The oxygen content of the mixed gas is about i% by volume or less, preferably about 0.6% by volume or less, and in the case of 1) (: + 111? Power, the oxygen content of the mixed gas is about 0.6% by volume or less, preferably about 0.4% by volume or less, and more preferably about 0.2% by volume or less. In the first step, the thickness of the ITO film as the first layer on the substrate is usually about 5 ~ About 100nm, preferably about 10 ~ about 70nm, most preferably about 15 ~ about 50nm In method B, the indium-tin oxide sintered body is used as a target, and this sputtering An ITO film formed on the first layer formed on the substrate and a second layer formed on the first layer (hereinafter, this step is referred to as a "second step"). The sputtering conditions in this second step are as follows. The type of power supply is DC power, RF power, or DC + RF power. When the applied power is a DC power supply, it is generally about 0 · ΐ to about 1 KW, and preferably about 0.3 to about 0.6 KW. The power of the RF power supply is generally about 0 to about 3 KW, and preferably about 1 to about 1.8 KW. In the case of DC + RF power, the power of the DC power is generally about 0.1 to about 1 KW, preferably about 0.2 to about 0.6 KW, and the power of the RF power is generally about 0.1 to about 3 KW, preferably about 0.2 to about 0.6 KW. . The DC / RF power ratio may be appropriately adjusted within a range of about 0.1 to about 10. When an RF power source is used, the frequency is usually about 6.78 to about 27 · 12 MHz, and preferably about 13.56 MHz. The temperature for forming the substrate of the first layer is usually from room temperature to less than 300 ° C, and preferably about 140 to 250 ° C. The sputtering gas is an inert gas. As the inert gas, a known inert gas can be widely used, and typical examples include a gas such as argon. -18- @ 张 码 量 Applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -0 tr --------- Economics Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau 521280 A7 _____ B7 V. Description of the invention (16) The gas pressure is usually about 0.1 to 1 P, and preferably about 0.2 to 0.8 Pa. The film thickness of the ITO film as the second layer formed on the first layer in the second step is usually about 5 to about 100 nm, preferably about 10 to about 70 nm, and most preferably about 30 to about 70 nm. In method B, secondly, the indium-tin oxide sintered body sintered body is used as a target 'this is in an inert gas or a mixed gas environment gas of inert gas and oxygen', and the second layer formed on the substrate is sputtered to A third layer of ITO film is formed on the second layer (hereinafter, this step is referred to as a "third step"). The sputtering conditions in this third step may be the same as those in the first step. The sputtering conditions in this third step are as follows. The type of power supply is DC power or DC + RF power. When the applied power is a DC power source, it is generally about 0.1 to about 1 KW, and preferably about 0.3 to about 0.6 KW. In the case of DC + RF power, the power of the DC power is generally about 0.1 to about 1 KW, preferably about 0.2 to about 0.6 KW, and the power of the RF power is generally about 0.1 to about 3 KW, preferably about 0.2 to about 2 0.6KW. The DC / RF power ratio may be appropriately adjusted within a range of about 0.1 to about 10. When an RF power source is used, the frequency is usually about 6.78 to about 27.12 MHz, and preferably about 13.56 MHz. The temperature of the substrate is usually near room temperature to less than 300. (:, Preferably about 140 to about 250 ° C. Sputtering gas is a mixed gas of inert gas and oxygen. Inert gas can be widely used as a known inert gas, and representative examples thereof include argon and the like. Gas. The gas pressure (sputtering pressure) is usually about 0.1 to 1P, preferably about 0.2 to -19. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)- ----------- Install --- (Please read the precautions on the back before filling out this page) · Thread & Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 521280 A7

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521280 A7 18 V. Description of the invention (In the present invention, both the power supply in step (1) and step (3) can be set as DC + RF power supply and the power supply in step (2) can be set as RF power supply. In this case, Steps (1) and (3) are performed under an ambient gas of an active gas or a mixed gas of inactive gas and oxygen, and step (2) is performed under an ambient gas of an inert gas. Further, (1) step and (3 The content of oxygen in the mixed gas of inactive gas and oxygen in step) is about 0.2% by volume or less. In the present invention, both the power supply in step (1) and step (3) can be dc power supply, and the power supply in step (2) The power supply is set to dc + RF power supply. In this case, step (丨) and step (3) can be performed under the environment gas of a mixture of inert gas and oxygen, and step (2) can be performed under the environment gas of inert gas. In addition, the oxygen content in the mixed gas of the inert gas and oxygen in step (1) and step (3) is about 0.1 to about 0.6% by volume or less. In the present invention, after the third step, Sputtering was performed under the same sputtering conditions as in the second step, and in the third step A fourth layer consisting of an IT0 film is formed on the transparent conductive film laminated substrate laminated with the ITO film of this four-layer structure, which is particularly excellent in terms of high conductivity and transparency. Moreover, a ιτο film structure with a four-layer structure is also possible. On the fourth layer of the laminated transparent conductive film laminated substrate, sputtering is performed under the same sputtering conditions as in the first step or the third step to form a fifth layer composed of an ITO film. The present invention can be repeatedly performed interactively The same sputtering conditions as in the second step and the same sputtering conditions as in the first step, and an ITO film with a thickness of 2 or more was formed on the fifth layer. In the method B, the temperature of the substrate was maintained at about 14 °. ~~ 25〇t & This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 public) ------- II--II · 1111111 ^ · 11111111 (Please read the precautions on the back before (Fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-21- A7 A7

V. Description of the invention (19) (Please read the precautions on the back before filling out this page) Three or more sputterings can be performed to form an ITO film composed of three or more layers on the substrate. In this case, since the temperature of the substrate is extremely low ', there is no risk of the substrate being deteriorated even if the ambient gas around the substrate is immediately returned to atmospheric pressure. The cooling can be completed in a short time in minutes. ○ Method B includes the following aspects. (B-1) Including: (1) Using a DC power supply or a DC + RF power supply, sputtering a target of an indium-tin oxide sintered body in an inert gas or a mixed gas of an inert gas and an oxygen gas, and Forming a first layer of ITO film on the substrate; (2) forming a second layer of ITO film on the first layer by sputtering the target in an inert gas atmosphere using a DC power supply or a DC + RF power supply; ; And (3) a step of forming a third layer of ITO film on the second layer by sputtering using the DC power supply or DC + RF power supply in the above target in an inert gas or a mixed gas of an inactive gas and an oxygen gas environment gas; Manufacturing method of transparent conductive film laminated substrate. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (B-2), as described in (B-1), the manufacturing method of the transparent conductive film laminated substrate is the combination of steps (1), (2), and (3). The power sources are all DC power sources (B-3). The manufacturing method of the transparent conductive film laminated substrate described in (B-2) is to mix steps (1) and (2) with inert gas and oxygen. It is carried out in a gas environment gas, and the step (2) is performed in an inert gas environment gas. 22- This paper size applies the Chinese National Standard (CNS) A4 specification (21〇X 297 public love) 52128〇Α7 _ Β7__ 5. Description of the invention (20) Proceed. (B-4). The method for manufacturing a transparent conductive film laminated substrate as described in (B-3) is that the oxygen content in the mixed gas of inert gas and oxygen in step (1) and step (3) is 1 Capacity% or less. (B-5) The method for manufacturing a transparent conductive film laminated substrate as described in (B-1), wherein the power supply in step (1) and step (3) is set to a DC power supply, and the power supply in step (2) is Set to RF power. (B-6) The method for manufacturing a transparent conductive film laminated substrate as described in (B-5), wherein the sputtering of steps (1) and (3) is performed in a mixed gas of inert gas and oxygen And the sputtering in step (2) is performed in an inert gas ambient gas. (B-7). The method for manufacturing a transparent conductive film laminated substrate as described in (B-6) is the oxygen content in the mixed gas of inert gas and oxygen in steps (1) and (3) is 1 Capacity% or less. (B-8) The method of manufacturing a transparent conductive film laminated substrate according to (B-5) is performed in steps (1), (2), and (3) under an inert gas atmosphere. (B-9), the manufacturing method of the transparent conductive film laminated substrate as described in (B-1) is to set the power supply of step (1) and step (3) to DC + RF power supply, and step (2) The power is set to rf power. (B-10), the method for manufacturing a transparent conductive film laminated substrate as described in (B-9), is performed in steps (1) and (3) in an inert gas and oxygen mixed gas environment gas, and Step (2) is performed in an inert gas ambient gas. -23- I paper size applies _7-round national standard (CNS) A4 specification (21〇χ 297 mm)-;--------------— (Please read the precautions on the back first Fill out this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 521280 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy A7 — ____B7 _ V. Description of the invention (21) (B — 11), such as (B-10 The method for manufacturing a transparent conductive film laminated substrate according to (2) is that the oxygen content in the mixed gas of the inert gas and oxygen in steps (1) and (3) is 0.2% by volume or less. (B-12) The manufacturing method of the transparent conductive film laminated substrate as described in (B-1) is to set the power supply in step (1) and step (3) to Dc power supply, and set the power supply in step (2) Set to DC + RF power. (B-13) The method for manufacturing a transparent conductive film laminated substrate as described in (B-12), wherein the steps (1) and (3) are performed in an inert gas and oxygen mixed gas environment gas, and Step (2) is performed in an inert gas ambient gas. (B-14) The method for manufacturing a transparent conductive film laminated substrate as described in (B-13), wherein the oxygen content in the mixed gas of inert gas and oxygen in steps (1) and (3) is 1 Capacity% or less. Method C: The method includes: (1) using a DC power source or a DC + RF power source, sputtering a target of an indium-tin oxide sintered body in an inert gas or a mixed gas of an inert gas and an oxygen gas, and sputtering the target on the substrate; A step of forming a first layer of a 1-butadiene film; and (2) using a DC power source, an RF power source, or a DC + RF power source to mix the target of an indium-tin oxide sintered body with an inert gas or an inert gas and oxygen A step of forming a second layer of a 1TO film on the first layer of a 1-but film by sputtering in a gas atmosphere. The characteristic of this method is that the target used in step (1) is indium-tin oxide. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) τ · —: --------- ------ Order --------- line (please read the precautions on the back before filling this page) • 24- 521280 A7 V. Description of the invention (22) 'Sintered body, used in ⑺ steps The dried seeds are indium oxide sintered bodies. The conditions are the same as Method A except that the dried seeds are different. According to the present invention, all the power sources in step (i) are set to DC power sources, and the power sources in step (2) are referred to as RF power sources. In this case, the step (2) can be performed under an inert gas and an ambient gas of oxygen = milk, and the step (2) is performed under a ring of inert gas. In addition, the oxygen content of the inert gas and oxygen gas in the step (i) is about ≤% by volume, and preferably about 0.6% by volume. The thickness of the IT0 film as the first layer formed on the substrate in step (1) is usually about 5 to about 100 nm, preferably about 10 to about 70 nm, and most preferably about 15 to about 50 nm. (2) The step of forming a film thickness of the indium oxide film as the second layer on the first layer is usually about 5 to about 100 nm, preferably about 10 to about 100 nm, and most preferably about 20 to about 100 nm. 70 nm. In the method c, the substrate is maintained at a temperature of about 140-1250 t & and a second sputtering is performed to form a ΠΌ film and an indium oxide film on the substrate. In this case, since the temperature of the substrate is extremely low, there is no risk of the substrate being deteriorated even if the ambient gas around the substrate is immediately returned to atmospheric pressure. Cooling can be completed in a short time in minutes. Method C includes the following aspects. (C-1) It has: (1) Using a DC power supply or a DC + RF power supply, the target of the indium-tin oxide sintered body is placed in an inert gas or a mixed gas of inert gas and oxygen. -25 · This paper size Applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) — — — — — — — — — — 11 (Please read the notes on the back before filling this page) i] · -Line · Ministry of Economic Affairs Intellectual Property Printed by the Bureau ’s Consumer Cooperatives 521280 A7 B7 V. Description of the Invention (23 Tibetan plating in an ambient gas, and the first layer is formed on the substrate] [Ding film, and, (2) DC power, RF power or DC + RF power supply, the step of forming a second layer of indium oxide film on the first layer by sputtering the indium oxide sintered body in an inert gas or an ambient gas of a mixed gas of inactive gas and oxygen to form a second layer of indium oxide film Manufacturing method of conductive film laminated substrate (C1-2), The manufacturing method of transparent conductive film laminated substrate as described in (C-1) is that the power source in step (1) is set to a DC power source and step (2) The power source is an RF power source. (C-3) The transparent conductive film as described in (A-2) The manufacturing method of the laminated substrate is that the steps (1) and (2) are performed in a mixed gas environment gas of inert gas and oxygen. (C1-4) The transparent conductive film as described in (C1-3) The manufacturing method of the laminated substrate is that (1) the oxygen content in the mixed gas of inert gas and oxygen in step 1 is 1% by volume or less, and the oxygen content in the mixed gas of inactive gas and oxygen in step (2) 0.6% by volume or less. (C-5) The manufacturing method of the transparent conductive film laminated substrate as described in (C-2) is the sputtering of the step (1) in a mixed gas of inert gas and oxygen. (C-6), the manufacturing method of the transparent conductive film laminated substrate as described in (C-5), is the step of (1) The content of oxygen in the mixed gas of inert gas and oxygen is less than 1% by volume. In addition to the above methods, the transparent conductive film laminated substrate of the present invention can be manufactured according to the following method D. -26- This paper size is applicable to China Standard (CNS) A4 Grid (210 X 297 mm) (Please read the precautions on the back before filling out this page)-Order --------- line wins the employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives printed the employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative 521280 Α7 _____ Β7 V. Description of the Invention (24) Method D: It has: (1) Using a DC power supply or a DC + RF power supply, the target of the indium-tin oxide sintered body is in an inactive gas or inactive The mixed gas of gas and oxygen is sputtered in the ambient gas to form the first layer of film on the substrate; (2) The DC target, RF power or DC + RF power is used to apply the above target in the inert gas environment gas. A step of pre-sputtering to form a second layer of ITO film on the first layer; and (3) using a DC power supply or a DC + RF power supply to dry the above-mentioned dry particles in an inert gas or a mixed gas of inert gas and oxygen Method for manufacturing a transparent conductive film laminated substrate in the step of forming a third layer IT0 film on the second layer by sputtering. The substrate and target used in this method are the same as method A. The conditions are the same as those of Method B, except that the sputtering ridge step is performed in an inert gas and oxygen mixed gas ambient gas. In the case of performing the steps (1), (2), and (3) under a mixed gas of inert gas and oxygen, the content of oxygen in the mixed gas of the inert gas and oxygen in the step is comparable to that in the step The oxygen content of the mixed gas in the same level or lower. Specifically, the oxygen content in the mixed gas of the inert gas and oxygen in step (3) and step (3) can be set to about 1% by volume or less, preferably about 0.2 to 0.6% by volume, and ( 2) The oxygen content in the mixed gas of the inert gas and oxygen in the step is set to about 0.3% by volume or less, preferably about 0.2 or less. In step (1), the thickness of the ιτ〇 film as the first layer is formed on the substrate. 11111111 „^^ I I I I — — I — I I I — I I (Please read the precautions on the back before filling this page) -27- A7

521280 V. Description of the invention (25) Often about 5 to about 100 nm, preferably about 10 to about 70 nm, and most preferably about 5 to about 50 nm. (2) is formed on the first layer as the first The film thickness of the 2-layer IT0 film is 5 to about 150 nm, preferably about 10 to about 100 nm, and most preferably about 20 to about 70 nm. The thickness of the iTQ film as the third layer is formed on the second layer in the step (3), usually about 5 to about 100 nm, preferably about 10 to about 70 nm, and most preferably about 15 to about 50. nm 〇 In the present invention, after the step (3), the sputtering can be performed under the same sputtering conditions as in the step (2), and a fourth layer composed of an IT0 film is formed on the third layer to Sputtering was performed under the same sputtering conditions as in step (1) or (3) to form a fifth layer composed of an ITO film. According to the present invention, the same sputtering conditions as those in step (2) and the same sputtering conditions as in step (1) can be repeatedly performed, and an ITO film of 1 or more can be formed on the fifth layer. In method D ', an ITQ film composed of three or more layers can be formed on the substrate by maintaining the temperature of the substrate at about 140-1250 t and performing sputtering three or more times. In this case, since the temperature of the substrate is extremely low ', there is no risk of the substrate being deteriorated even if the ambient gas around the substrate is immediately returned to atmospheric pressure. The cooling can be completed in a short time in minutes. The method D includes the following aspects. (D-1) Contains: -28- The size of this button conforms to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) " "-(Please read the precautions on the back before filling this page)

P π --------- line! Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 521280 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The mixed gas is sputtered in an ambient gas to form a first layer of a 1 butyl film on the substrate; (2) using a DC power source, an RF power source, or a DC + RF power source to mix the above-mentioned dried seeds in an inert gas and oxygen and fluorine; The step of applying a base bond in the ambient gas of the gas to form a second layer of ITO film on the first layer, and (3) using a DC power source or a DC + RF power source to place the above target in an inactive gas or inactive gas and A method for manufacturing a transparent conductive film laminated substrate in the step of forming a third layer of ITO film on the second layer by applying a base plating to a mixed gas of oxygen in an ambient gas. (D-2), as described in (D-1) The manufacturing method of the transparent conductive film laminated substrate is to set the power supply of the steps (1), (2) and (3) to DC power supply. (D — 3) The transparent conductive film as described in (D — 2) The manufacturing method of laminated substrates is (1) step Steps (2) and (3) are performed in a mixed gas environment gas of inert gas and oxygen < gas. (D-4) Manufacturing method of transparent conductive film laminated substrate as described in (D-3) 'It is the mixed gas of inactive gas and oxygen in steps (1) and (3) _ The content of oxygen in the body is less than 1% by volume, and the oxygen content of the mixed gas of inactive gas and oxygen in step (2) The amount is less than 0.3% by volume. (D-5), the manufacturing method of the transparent conductive film laminated substrate as described in (D-4) is the inert gas and oxygen in steps (1) and (3) The oxygen content in the mixed gas is about 0.2 to about 0.6% by volume, and the oxygen content in the mixed gas of the inert gas and oxygen in step (2) is 0.2 to -29. This paper size Applicable to China National Standard (CNS) A4 (210 X 297 mm) I · I I --- II — II --- · Cord (Please read the precautions on the back before filling this page) 521280 A7

5. Description of invention: (27)% or less. (Please read the precautions on the back before filling in this page) (D-6), The manufacturing method of the transparent conductive film laminated substrate as described in (D ~ 1) is the power supply of step (1) and step (3) Both are set to Dc power supply, and the power supply in step (2) is set to RF power supply. (D-7), the manufacturing method of the transparent conductive film laminated substrate as described in (D ~ 6), is the step (1) and ( 3) The step is performed in an inert gas ambient gas, and the step (2) is performed in a mixed gas ambient gas of inert gas and oxygen. (D-8) The transparent conductive film as described in (D-7) The manufacturing method of the laminated substrate is that the oxygen content in the mixed gas of the inert gas and oxygen in the step (2) is 1% by volume or less. (D-9) The transparent conductive film laminate as described in (D-8) The manufacturing method of the substrate is that the oxygen content in the mixed gas of the inert gas and oxygen in the step (2) is 0.3% by volume or less. The sputtering method in the above methods A to D is a well-known sputtering method and includes, for example, sputtering Magnetron sputtering, reactive sputtering, ECR sputtering, etc. Manufacturing of filters: Ministry of Economic Affairs The employee's cooperative of the Bureau printed the color filter of the present invention by forming a light-shielding film, a color photoresist film, and an ITO conductive film on a transparent substrate. It can also be protected between the color photoresist film and the ITO conductive film. The transparent substrate is not limited, and a transparent substrate generally used in this field can be widely used. Specific examples of the transparent substrate include glass plates such as alkaline glass and alkali-free glass, polycarbonate, and polymethacrylic acid. Resin plates such as esters. Among these materials, alkali-free resin is preferred. The size and thickness of the transparent substrate is -30. ^ The size is suitable. ^ China National Standard (CNS) A4 specification (210 X 297 mm). Printed by the Consumer Cooperative of the Property Bureau 521280 A7 ----——--- E __— _ V. Description of invention (28) The degree can be appropriately selected according to the purpose of use of the color filter. The material forming the light-shielding film can be widely A light-shielding film material commonly used in this field is used. Examples of the material for forming the light-shielding film include metals, metal oxides, and resins that disperse pigments. As the metal, specifically, chromium, molybdenum, titanium, aluminum, and the like are used. Metal Of Specific examples of the oxide include chromium oxide, aluminum oxide, and the like. Specific examples of resins for dispersing pigments include carbon-dispersed resins, black pigment / dispersion resins, and the like. Among these resins are barriers, film-forming properties, etc. Viewpoints • It is better to use metallic chromium, chromium oxide, carbon dispersing resin, and black pigment dispersing resin. The materials used to form color photoresist films can be widely used as color photoresist film forming materials commonly used in this field. Color photoresist Examples of the agent film-forming material include acrylic resin, polyester resin, polyvinyl alcohol resin, polyimide resin, or a mixture of these resins to disperse red, green, or blue colorants. As the resin constituting the protective layer, resins commonly used in this field can be widely used, and examples thereof include epoxy resin, acrylic resin, and polyimide resin. When a light-shielding film, a color photoresist film, and a protective film are formed on a transparent substrate, known light-shielding film formation methods, color photoresist film formation methods, and protective film formation methods can be widely used. The color filter of the present invention can form at least two layers of an ITO conductive film on a light-shielding film and a color photoresist film, and on a transparent substrate forming a protective film as necessary. The color filter of the present invention forms a light-shielding film and a color photoresist film on a transparent substrate by a well-known method, and further forms a protective film as necessary. -31- This paper standard applies to China National Standard (CNS) A4 (210 X 297 mm) ------------- install -------- order --------- line (please read the precautions on the back before filling (This page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 521280 A7 ---------- B7____ V. Description of the invention (29) ^ " After 'in any of the above methods A ~ Method E conductive film The formation method produces a conductive film. The manufacturing method of the transparent conductive film laminated substrate according to the present invention can improve the carrier (free electron) density in the conductive film, and can hardly reduce the carrier mobility or maintain the carrier mobility or improve the carrier mobility. Therefore, a transparent conductive film laminated substrate having high conductivity can be obtained. Since the conductive film formed on the substrate has high conductivity, it is not necessary to make the film thick to ensure excellent transparency. Therefore, according to the present invention, a transparent conductive film laminated substrate having high electrical conductivity, that is, small electrical resistivity can be manufactured. According to the present invention, a transparent conductive film laminated substrate having excellent transparency can be manufactured. In the method of the present invention, it is not necessary to maintain the substrate condition at a temperature of more than 300c, and depending on the situation, a good conductive film can be formed on the substrate even at a relatively low temperature of 14 ~ 25 {rc. . Therefore, the types of substrates used are not limited. The method of the invention need not necessarily be from 300 under vacuum. The temperature above 匸 is lower than 250 ° C, so it is practical. The method of the present invention can change a type of a power source and a sputtering gas during sputtering to form a desired ITO film on a substrate, and therefore has industrial applicability. The method of the present invention is extremely practical because it does not require special treatment such as tempering treatment. According to the present invention, a color filter having a high conductivity, that is, an ITO conductive film having a low resistivity can be manufactured. According to the present invention, it is possible to produce a color doped sheet having excellent transparency. [Best implementation of the invention] 32- " ^ 's scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) --- τ: 41 ^ -------- tr --------- Line (Please read the notes on the back before filling out this page) 521280 A7 B7 V. Description of the Invention (3Q) The following examples and comparative examples are given to further explain the present invention. An example of manufacturing a transparent conductive film laminated substrate is shown below. (Please read the note on the back? Matters before filling out this page.) The operations in the examples and comparative examples below are outlined as follows. A glass substrate (200 mm x 260 mm, thickness 0.7 mm) was set in a preheating zone, and preheated under vacuum to a certain temperature for 60 minutes. Once the substrate is preheated to a certain temperature, argon and oxygen are introduced into the gas at a certain ratio. After adjusting the full pressure (sputtering pressure) to 0.7 Pa, a certain power source is applied to the target to start discharging. After confirming that the glow discharge on the stem is stable, the substrate is moved during discharge at a moving speed of 1.0 m / min, and a first layer of transparent conductive film having a certain thickness is formed on the substrate. Back and forth on the dried seeds until a certain film thickness is formed. Next, argon and oxygen are introduced into the gas at a certain ratio, and after adjusting the total pressure to a certain pressure, a certain power source is applied to the target to start discharging. After confirming that the glow discharge on the target is stable, the preheated substrate is moved during the discharge at a moving speed of 10 m / min, and a substrate with a certain thickness printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is formed on the substrate 2 layers of transparent conductive film. Go back and forth on the target until a certain film thickness is formed. When the third transparent conductive film and the fifth transparent conductive film are formed on the second transparent conductive film, the same operations as those for forming the first transparent conductive film are repeated. In the case where the fourth transparent conductive film is formed on the third transparent conductive film, the same operations as those for forming the second transparent conductive film are repeated. • 33- This paper is printed in Chinese National Standard (CNS) A4 specification (⑽χ 挪 公公 爱) Printed by the Intellectual Property Bureau of the Ministry of Economy, Employee Consumer Cooperatives 521280 A7 _B7_ V. Description of the invention (31) In addition, the glass substrate after film formation is moved Go to the vacuum chamber, and after cooling for three minutes, replace the substrate from the vacuum chamber with nitrogen, and take out the glass substrate on which the transparent conductive film has been formed. A sintered body of indium-tin oxide (tin oxide content 10 wt. %, The same applies hereinafter) The target is sputtered to form a first layer (film thickness: 438.8 persons) made of an ITO film on a glass substrate maintained at 200 ° C. Next, an indium-tin oxide sintered target was sputtered under an argon gas (sputtering pressure 0.7 Pa) using an RF power source (electric power 1.5KW, frequency 13.56MΗζ) to form a layer on the first layer. The second layer (film thickness: 438.8 persons) made of ITO film to obtain the transparent conductive film laminated substrate of the present invention. Comparative Example 1: An indium-tin oxide sintered body target was sputtered using an RF power source (electron 1.5KW, frequency 13.56MHz) under an atmosphere of argon (sputter pressure 0.7Pa) and maintained at 200 ° C. A first layer made of an ITO film (film thickness: 553.9 persons) was formed on a glass substrate. Next, an indium-tin oxide sintered target was sputtered using a DC power supply (electricity 0.5KW) under an ambient gas of a mixed gas of argon and oxygen (oxygen content of 0.542% by volume and sputtering pressure of 0.7Pa). A second layer (film thickness: 553.9 mm) made of ITO film was formed on the first layer by plating to obtain a conductive film laminated substrate. The sheet resistance of the transparent conductive film laminated substrate of the present invention obtained in Example 1 and the conductive film laminated substrate obtained in Comparative Example 1 was determined. -34- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order ------ --- Line Qin 521280 A7 B7 V. Description of the invention (32) The sheet resistance is obtained in the following way. That is, 67 measurement points were uniformly set on the film surface formed on a glass substrate having a thickness of 200 mm x 260 mm and a thickness of 0.7 mm, and a four-probe resistance meter (MCP I-Ding 600) manufactured by Mitsubishi Chemical was used to obtain the measurement points. Resistance value, and find these average values, and multiply by constant = 4.5424 to find sheet resistance. The film thickness was determined as described below. That is, the two-dimensional fine shape measuring device (ET4000) manufactured by Kosaka Research Institute was used to measure the film thickness of the conductive film formed on the glass substrate. The measurement was performed by setting 5 measurement points on a glass substrate, and masking with a force: / bubble. After the film was formed, the mask was peeled off and the film thickness was measured. The average value was used as the film thickness of the film. The resistivity (Ω · cm) can be obtained by multiplying the sheet resistance value obtained by the above-mentioned four-probe method by the film thickness. The transmittance (%) of the transparent conductive film laminated substrate of the present invention obtained in Example 1 and the conductive film laminated substrate obtained in Comparative Example 1 was determined. That is, the transmittance (%) of the conductive film laminate substrate and the transmittance (%) of the glass substrate (blank) before film formation were measured using a spectrophotometer (u-2010) manufactured by Yueli Manufacturing Co., Ltd. ) Is set to calculate the transmittances (%) at 62 nm, 540 nm, and 460 nm. The results are shown in Table 1. Table 1 (continued on next page) -35- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) — — — — — — — — — — — — (I read first Note on the back, please fill out this page again) Order · --- Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 521280 A7 B7 V. Description of the invention (33) Full film of transparent conductive film (A) Sheet resistance (Ω / □ ) Resistivity and transmittance (%) (Ω cm) 620nm 540η m 460nm Example 1 877.5 17.80 1.54x 10-4 90. 13 89. 0 5 91.82 Example 2 1107.8 27, 01 2.99x 10-4 90. 17 92.6 2 93.97 (Please read the precautions on the back before filling out this page) Example 2: Under the ambient gas of mixed rolling body of argon and oxygen (oxygen content GW capacity%, splash pressure 0 · 7Pa), Using a Dc power source (electricity: 0, the indium-tin oxide sintered body was dried and the first layer (film thickness 433A) made of a ιτο film was formed on a glass substrate maintained at 20 (rc). Next, argon was used. Gas (money pressure 0.7Pa), using a π power source (electricity 0.5KW) to indium-tin oxide sintered body target A second layer (film thickness 433A) made of ITO film was formed on the first layer by sputtering. Next, a mixed gas of argon and oxygen (oxygen content 0.54% by volume, sputtering pressure 0 · 7Pa), using a DC power supply (power 0.5KW) to sputter the indium-tin oxide sintered body target to form a third layer (film thickness 433A) made of IT0 film on the second layer. In order to obtain the transparent conductive film laminated substrate of the present invention. Comparative Example 2 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs.... Under an argon gas (sputter pressure 0.7Pa), a DC power supply (electricity 0KW) is used. A target of indium-tin oxide sintered body was sputtered and maintained at 2⑼. [The glass substrate was formed with a single layer composed of ITO film (Ki thickness 1686 · 6A) to obtain a conductive film laminated substrate. 36.

Wood paper scale is applicable to Chinese national standard Muorvr VIII, iT < U 1 r c / VJ r 1) \

~ Full film of transparent conductive f (person) Sheet electricity f (Ω / □) [Resistance value ~ Transmittance (%) (Ω · cm) 620nm 540η m 460η m Example 1 1299. 1 13. 37 1. 74 X ΐ0.495. 16 97. 9 1 91. 2 1 Example 2 1686.6 15. 30 2. 58 X 10- 4 90. 16 90. 9 6 83. 8 5 Example 3 1504.3 15. 64 ^ 2. 35Χ ΙΟ- 4 96. 55 98. 0 1 88. 2 0 Example 3: 521280 5. Description of the invention (Comparative Example 3: A mixed gas of oxygen read in a rat (oxygen content of 0.54% by volume, base plating dust) (7 · Pa), the power source (whatever the power is) will be indium-tin oxide sintering plant body dry plating to maintain 2 ⑽. C on the glass substrate is formed: a single layer composed of jin ( Film thickness 504 × 3) to obtain a conductive film laminated substrate. For the transparent conductive film laminated substrate of the present invention obtained in Example 2 and the conductive film laminated substrate obtained from Comparative Examples 2 and 3, and The sheet resistance value (Ω · □), resistivity (⑴ · cm), and the transmittance (%) of the Group 6 claw, so-called thin, and young nm were obtained in the same manner as described above. Table 2 The indium-tin oxide sintered body was dried using an dc power source (electricity 0.5 KW) under an ambient gas of a mixed gas of rat gas and oxygen (oxygen content of 0 542% by volume and a low pressure of 0 · 7Pa). The child reduced the amount of money and formed the first layer made of ITO film on the glass substrate maintained at 20 (with a thickness of 446 5 people). Secondly, under the environment gas of argon G (plating pressure 0.7Pa), use RF power supply -37- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 male β ":------- ------ -Install ----------- Order 1! 111 line (please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 521280 A7 _B7_ V. Invention Explanation (35) (electricity 1.5 KW, frequency 13. 56 MHz) The indium-tin oxide sintered target is sputtered to form a second layer (film thickness 446.5) composed of ITO film on the first layer. Please read the precautions on the back before filling in this page) A). Next, use a DC power supply (electricity 0.5KW) under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa). ) Sputtering an indium-tin oxide sintered body target to form a third layer (film thickness: 446.5 people) composed of an ITO film on the second layer to obtain the transparent conductive film laminated substrate of the present invention. Example 4 · DC power supply is used in an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa) Power: 0.5KW) The indium-tin oxide sintered target was sputtered to form a first layer (film thickness 177.8 A) made of ITO film on a glass substrate maintained at 200 ° C. Next, argon (sputter Under an ambient gas of 0.7 Pa), an indium-tin oxide sintered target was sputtered using an RF power source (electric power 1.5 KW, frequency 13. 56 MHz) to form a first layer made of an ITO film on the first layer. 2 layers (film thickness 177.8 A) 〇 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, followed by an argon and oxygen mixed gas (oxygen content 0.542% by volume, sputtering pressure 0.7Pa) under ambient gas Using a DC power supply (power 0.5KW), an indium-tin oxide sintered target was sputtered to form a third layer (177 · 8A) made of an ITO film on the second layer. Next, argon (sputtering Under an ambient gas pressure of 0.7 Pa), an indium-tin oxide sintered body target was sputtered using an RF power source (electric power 1.5 KW, frequency 13. 56 MHz) to form a third layer made of an ITO film on the third layer. Layer (film thickness 177.8 -38-) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 521280 A7 B7 V. Description of Invention (36) A). Next, in a gas mixture of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa), a DC power supply (electricity 0.5KW) was used to sputter the indium-tin oxide sintered target and A fifth layer made of an ITO film (with a film thickness of 177.8 persons) was formed on the fourth layer to obtain the transparent conductive film laminated substrate of the present invention. Example 5: A target gas of indium-tin oxide sintered body was produced using a DC power supply (electricity 0.5KW) under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa). 1A。 Sputtered to form a first layer (film thickness 182.1 1A) composed of an ITO film on a glass substrate maintained at 200 ° C. Next, an indium-tin oxide sintered body target was sputtered under an argon gas (sputtering pressure 0.7Pa) using an RF power source (electric power 1.5KW, frequency 13.56MHz) to form a layer on the first layer. The second layer of ITO film (455.3 film thickness). Next, an indium-tin oxide sintered target was sputtered using a DC power source (electricity 0.5KW) under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa). A third layer (film thickness 182.1A) made of an ITO film is formed on the second layer to obtain the transparent conductive film laminated substrate of the present invention. Example 6: In an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa), a DC power source (electricity 0.5KW) was used to target an indium-tin oxide sintered body Glass substrate that is sputtered and maintained at 299 ° C-39- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ^ ------- I ^ ------ --- ^ (Please read the precautions on the back before filling out this page) 521280 A7 B7 V. Description of the invention (37) The first layer of Π0 film (film thickness 208 people) is formed on the board. (Please read the precautions on the back before filling in this page.) Next, sinter indium-tin oxide under an argon gas (sputter pressure: 0.7Pa) using an RF power source (power: 1.5KW, frequency: 13.56MHz). The target is sputtered to form a second layer (film thickness: 519. 9 A) composed of ITO film on the first layer. Secondly, a mixed gas of argon and oxygen (oxygen content: 0.542% by volume, sputtering Under the ambient gas of 0.7Pa), a DC power supply (0.5KW power) was used to sputter the indium-tin oxide sintered target to form a third layer (208A) composed of ITO film on the second layer. To obtain the transparent conductive film laminated substrate of the present invention. For the transparent conductive film laminated substrate of the present invention obtained in Examples 3 to 6, the sheet resistance value (Ω · □), resistivity (Ω · cm), and transmittances of 620nm, 540nm, and 460nm were obtained in the same manner as above. %). The results are shown in Table 3. Table 3 Sheet resistivity, resistivity, transmittance (%), full film thickness (A) (Ω / (Q · cm) 620nm 540η m 460nm Example 3 1339.5 12. 36 1. 65X 10 '4 94. 93 98. 2 9 93. 67 Example 4 888. 8 16. 70 1 · 48X 10-4 89. 96 89. 9 9 94. 06 Example 5 819. 5 18. 43 1. 51 X 10) 4 89. 45 88. 2 9 90. 65 Example 6 935.8 15. 52 1.45X10- 4 92. 38 90. 4 5 91. 58 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 7: -40- This paper standard applies China National Standard (CNS) A4 specification (210 X 297 public love) 521280 A7 B7 V. Description of the invention (38) In addition to the second layer of sputtering on the first layer, a mixed gas of argon and oxygen (oxygen A transparent conductive film laminate substrate of the present invention was obtained in the same manner as in Example 3 except that the content was 0.542% by volume and the sputtering pressure was 0.7 Pa). The first layer and the second layer formed on the substrate The third layer is 488. 1 person. Example 8: Except that the second layer is sputtered on the first layer, a mixed gas of argon and oxygen (oxygen content 0.542% by volume, coin plating pressure) The transparent conductive film laminated substrate of the present invention was obtained in the same manner as in Example 3 except that the process was performed under an ambient gas of 0.07 Pa). The first layer, the second layer, and the third layer formed on this substrate were all 432.1 For the transparent conductive film laminated substrates of the present invention obtained in Examples 7 and 8, the sheet resistance value (Ω · □), specific resistance (Ω · cm), and transmission at 620 nm, 540 nm, and 460 nm were obtained in the same manner as described above. The results are shown in Table 4. The sheet resistivity and transmittance of the transparent conductive film in Table 4 (%) Full film thickness (A) (Ω / □) (Ω · cm) 620nm 540η m 460η m Example 7 1464.2 12.36 1. 81 X i〇- 4 95. 47 98. 6 9 92. 5 8 Example 8 1296.2 13. 92 1.80 X 10-4 93. 10 97. 7 9 97. 2 0 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ----------------- (Please read the precautions on the back before filling this page)-Line · Example 9: In Argon In an ambient gas mixture of gas and oxygen (sputtering pressure: 0.7Pa), sintering of indium-tin oxide was performed using a DC + RF power supply (DC: 0.4KW, RF: 0.4KW, frequency: 13.56M56ζ). The target is sputtered and the ITO film is formed on -41- this paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) 521280 A7 B7_______ V. Description of the invention (39) A glass substrate maintained at 200 ° C The first layer formed (film thickness 451.9A). Next, an indium-tin oxide sintered body target was sputtered under an argon gas (sputter pressure 0.7Pa) using an RF power source (electricity 1.5KW, frequency 13.56MHz) to form a layer on the first layer. The second layer of ITO film (film thickness: 45 · 9 A) 〇Then use dc + RF power source (DC: electric power 0.4KW, RF _ · electric power under an argon gas (sputter pressure 0.7Pa) ambient gas) 0.4KW, frequency 13.56MHz) sputtered the target of indium-tin oxide sintered body to form a third layer (film thickness 451.9 people) composed of 1T0 film on the second layer to obtain the transparency of the present invention Conductive film laminated substrate. Example 10: In addition to sputtering on which a first layer is formed on a glass substrate, and sputtering on which a third layer is formed on a second layer, a mixed gas of argon and oxygen (oxygen content of 0.18% by volume, sputtering A transparent conductive film laminated substrate of the present invention was obtained in the same manner as in Example 9 except that the plating pressure was performed under an ambient gas of 0.7 Pa). The film thickness of the first layer, the second layer, and the third layer formed on this substrate was 470.6A. The results are shown in Table 5. (Please read the notes on the back before filling this page)

Sheet No. 5 of the transparent conductive film printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Transmittance (%) of the sheet resistivity. --- Full film thickness (A) (Q / □) (Ω · cm) 620nm 540η m 460η m Example 9 ^ ----- 1355. 7 11. 34 1 · 54X 1〇4 95 · 79 98. 2 4 92. 3 4 Example 10 1411 · 9 12 · 51 1 · 77 X 104 0 97 22 99. 3 9 91. 8 1 -42- Specifications (210x 297 mm) The paper size of the paper (eNS) A4 521280 A7 B7 V. Description of the invention (4G) Example 11: Mixing argon and oxygen In an atmosphere of gas (oxygen content 0.542% by volume, sputtering pressure 0.7Pa), a DC power source (electricity 0.5KW) was used to sputter the indium-tin oxide sintered target while maintaining the glass at 200 ° C. The first layer (film thickness 467.5 people) composed of an ITO film was formed on the substrate. Next, an indium-tin oxide sintered target was RF-powered (electric power 1.5KW, frequency 13.56MHz) under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume and sputtering pressure 0.7Pa). 5A) Sputtered to form a second layer (film thickness 467.5 5A) composed of an ITO film on the first layer. Next, an indium-tin oxide sintered target was sputtered using a DC power source (power 0.5KW) under an ambient gas of a mixed gas of argon and oxygen (oxygen content of 0.542% by volume and sputtering pressure of 0.7Pa). A third layer (film thickness 467.5 A) made of an ITO film is formed on the second layer to obtain the transparent conductive film laminated substrate of the present invention. Example 12: An indium-tin oxide sintered body target was sputtered on a glass substrate maintained at 20 (TC) using an argon gas (sputter pressure: 0.7 Pa) using a DC power source (power: 0.5 KW). The first layer (film thickness 470.8 A) made of ITO film was formed. Secondly, DC was used under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume and sputtering pressure 0.7Pa). Power source (power: 0.5KW) The indium-tin oxide sintered body target was sputtered to form a second layer made of an ITO film (with a film thickness of 478.8 persons) on the first layer. Next, argon (sputtering Use DC power supply under ambient gas pressure of 0.7 Pa) -43- This paper size applies to China National Standard (CNS) A4 (210 χ 297 mm) --- (Please read the precautions on the back before filling this page ) Γ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 521280 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () (Electricity 0.5KW) The target of indium-tin oxide sintered body was placed on A third layer (a film thickness of 470.8 persons) made of an ITO film was formed on the second layer to obtain The transparent conductive film laminated substrate of the invention. For the transparent conductive film laminated substrate of the present invention obtained in Examples 11 and 12, the sheet resistance value (Ω · □), the specific resistance ⑴ · cm) ′, and the 620 nm and 540 nm were obtained in the same manner as described above. And 460nm transmittance (%). The results are shown in Table 6. Table 6 Sheet resistivity, resistivity, transmittance (%) of the transparent conductive film, full film thickness (Α) (Ω / □) (Ω · cm) 620nm 540η m 460η m Example 11 1402 · 4 19. 22 2. 70X 10 & quot 4 93. 84 98. 7 0 93. 3 6 Example 12 1412 · 3 19. 28 2. 72 × 10 '4 95. 63 99. 7 7 92. 8 4 Example 13: Mixing with argon and oxygen In an atmosphere of gas (oxygen content of 0.36% by volume and sputtering pressure of 0.28Pa), a DC power supply (electricity 0.5KW) was used to sputter the indium-tin oxide sintered target while maintaining the temperature at 15 ° C. 5A) A first layer made of an ITO film was formed on a glass substrate. Next, an indium-tin oxide sintered body target was sputtered using an RF power source (electric power 1.5KW, frequency 13.56MHz) under an ambient gas of argon (sputtering pressure 0.28Pa) to form a layer on the first layer. The second layer of ITO film (thickness 673, 3 A). To obtain the transparent conductive film laminated substrate of the present invention. Comparative Example 4: This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ^; --------------- Order --------- Line ^ 一 ^ (Please read the precautions on the back before filling out this page) 521280 A7 B7 V. Description of the invention (42) In a mixed gas of argon and oxygen (oxygen content: 0.542% by volume, sputtering pressure: 0.7Pa) ) In the ambient gas, using a dc power supply (power 0.5KW) to sputter the indium-tin oxide sintered target to form a first layer (film) made of ITO film on a glass substrate maintained at 50 ° C. 1069 · 2A) to obtain a conductive film laminated substrate. Comparative Example 5: An indium-tin oxide sintered body target was sputtered under an argon gas (sputtering pressure of 0.7 Pa) using a DC power source (power 0.5 KW) and maintained at a temperature of 500 ° C. A single layer (film thickness: 928 · 0) made of a ιτο film was formed on a glass substrate to obtain a conductive film laminated substrate. Comparative Example 6: Indium-tin oxide was sintered using a DC power source (electricity 0.5 kw) under an ambient gas of a mixed gas of argon and oxygen (oxygen content of 036% by volume and sputtering pressure of 0 · 7Pa). The bulk target is sputtered to form a single layer (film thickness: 1406.5 people) made of ITO film on a glass substrate maintained at 150 ° C to obtain a conductive film laminated base ------------ -Installation— (Please read the precautions on the back before filling this page) Printed Line Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Comparative Example 7: Use dc under ambient gas of rat gas (money pressure 0.7Pa) + rf power supply (DC · Power 0.4KW, RF: Power 0.4KW, Frequency 13.56MΗζ) Sputtering an indium-tin oxide sintered body target to form an ITO film on a glass substrate maintained at 150 ° C Single layer (film thickness 1420 · 2 persons). To obtain a conductive film laminated substrate. For the transparent conductive film laminated substrate of the present invention obtained in Example 13 and the conductive film laminated substrate obtained in Comparative Examples 4 to 7, the sheet electricity was obtained in the same manner as described above. -45- This paper applies the Chinese National Standard (CNS) A4 Specifications (21 (^ 297 mm) 521280 A7 B7 V. Description of the invention (43) Resistance (Ω · □), resistivity (Ω · cm) 'and transmittances (%) at 620nm, 540nm, and 460nm. Results As shown in Table 7. Sheet Resistivity, Resistivity, and Transmittance of the conductive film in Table 7 (%) Full film thickness (A) (Ω / □) (Ω · cm) 620nm 540η m 460η m Example 13 961. 8 17 56 1. 69X 10 ~ 4 88. 52 89. 9 8 94. 8 8 Comparative Example 4 1069.2 40. 76 4. 36X 10 '4 88. 14 90. 6 3 95. 9 9 Comparative Example 5 928. 0 35 62 3. 31 X 10 '4 87. 10 87. 9 2 90. 4 1 Comparative Example 6 1406.5 21. 64 3. 04X 10' 4 97. 58 100 · 0 89. 7 3 Comparative Example 7 1 1420.2 23. 96 3. 40X 10 '4 98. 32 99. 9 4 87. 7 9 Example 14 · Under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.36% by volume, sputtering pressure 0.28Pa), DC power (0.5KW) is used to convert indium-tin oxide The sintered body target is sputtered to form a first layer (film thickness 308.6 A) made of an ITO film on a glass substrate maintained at 15 ° C. Next, an atmosphere of argon (sputter pressure 0.28 Pa) is used. 0, using an RF power source (electric power 1.5KW, frequency 13.56MHz) to sputter the indium-tin oxide sintered target to form a second layer (film thickness 720.0) made of an ITO film on the first layer A) 〇 Next, indium-46 · is used in a mixed gas of argon and oxygen (oxygen content 0.36% by volume, sputtering pressure 0.28Pa) using a DC power supply (electricity 0.5KW). Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) Order --------- Printed by the Consumer Consumption Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 521280

V. Description of the invention (44)-a tin oxide sintered body target is sputtered to form a third layer (thickness 308.6 6A) composed of an ITO film on the second layer, followed by argon (sputtering pressure. 28Pa), an indium-tin oxide sintered target was sputtered using an RF power source (electric power 1.5KW, frequency 13.56MHz) to form a fourth layer (ITO film) on the third layer ( The film thickness is 720.0 A) to obtain the transparent conductive film laminated substrate of the present invention. The sheet resistance value (Ω · □) was calculated in the same manner as above, and the resistivity (Ω · cm) was 1.84 X 1 0-4. The transmittances (%) at 620nm, 540nm, and 460nm were 91.1% and 87.0%, respectively. , 93.7%. For some of the representative transparent conductive film laminated substrates obtained above, the electrical characteristics (carrier density and mobility) of the conductive film are shown in Table 8. The carrier density and mobility of the conductive film are measured at 23 ° C using Resi Test 8320 manufactured by Toyo Yukiji (Limited). Table 8 (continued on next page) ---------------- I (Please read the notes on the back before filling out this page) Order · Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 521280 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (45) Carrier density (pcs / c m3) Mobility ( cm 2 / V sec) Example 1 9. 9 3 X 1 0 20 4 1. 7 Comparative Example 17. 2 1 X 1 0 20 3 3. 7 Example 2 8. 8 5 X 1 0 2 0 4 1.6 Example 5 1. 0 4 X 1 0 21 4 2. 1 Example 9 9. 6 1 X 1 0 20 4 5 8 Example 10 8. 3 6 X 1 0 20 45.8 Example 13 1. 0 6 X 1 0 2 1 4 1. 1 Comparative Example 4 5. 9 9 X 1 0 20 2 6.0 Comparative Example 7 5. 5 1 X 1 0 20 3 3. 7 Example 14 9. 9 1 X 1 0 20 4 0. 1 Next, a manufacturing example of a color filter will be described. A glass substrate (200 mm X 260 mm, thickness 0.7 mm) formed with a light-shielding film, a color photoresist film, and a protective layer was used instead of the glass substrate (200 mm X 260 mm, thickness 0.7 mm). Color filter for laminated transparent conductive film. Example 15: An indium-tin oxide sintered target was applied using a power source (electricity 0.5 kw) under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0 · 7Pa). Sputtering was maintained at 200. On the glass substrate on which the light-shielding film, the color photoresist film, and the protective layer have been formed, a first layer (film thickness 262.0A) made of the IT0 film is formed. Next, use an RF power supply under an argon gas (sputter pressure 0.7Pa).

T ---: --------------- Order --------- (Please read the precautions on the back before filling out this page) Staff Consumption of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the cooperative 521280 A7 B7 V. Description of the invention (46) (electric power 1.5KW, frequency 13.56MHz) The indium-tin oxide sintered body target is sputtered to form a second layer consisting of an ITO film on the first layer Layer (film thickness 611.4 A) 〇 Next, indium gas was mixed with argon and oxygen gas (oxygen content 0.542% by volume, sputtering pressure 0.7Pa) using a DC power supply (power 0.5KW) to indium A tin oxide sintered body target is sputtered to form a third layer (film thickness: 262.0 people) composed of an ITO film on the second layer to obtain the color filter of the present invention. Example 16 In a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa), an indium-tin oxide sintered body was DC-powered (electricity 0.5KW). The target is sputtered and a first layer (thickness: 232. 9A) made of an ITO film is formed on a glass substrate having a light-shielding film, a color photoresist film, and a protective layer maintained at 200 ° C. Next, an indium-tin oxide sintered body target was sputtered under an argon gas (sputter pressure: 0.7 Pa) using an RF power source (electric power: 1.5 KW, frequency: 13. 56 MHz) to form on the first layer. 8 A)。 The second layer composed of ITO film (film thickness 698.8 A). Next, an indium-tin oxide sintered target was sputtered using a DC power source (power 0.5KW) under an ambient gas of a mixed gas of argon and oxygen (oxygen content of 0.542% by volume and sputtering pressure of 0.7Pa). A third layer (thickness: 232.9A) made of an ITO film is formed on the second layer to obtain the color filter of the present invention. Comparative Example 8: An indium-tin-49- is used in a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa) using a DC power supply (electricity 0.5KW) China National Standard (CNS) A4 Specification (210 X 297 mm) ------------- Installation -------- Order --------- Line (Please (Please read the notes on the back before filling out this page) 521280

The oxide sintered body was sputtered to form a single-layer film (film thickness 1133 ·) made of an IT0 film on a glass substrate having a light-shielding film, a color photoresist film, and a protective layer maintained at 200 ° C. OA) to obtain a color filter. Comparative Example 9: Indium-tin oxide was sintered using a DC + RF power source (DC · electric power 0.4 KW, RF: electric power 0.4 KW, frequency 13.56 MHz) under an ambient gas of argon gas (base plating pressure 0.7 Pa). The body target is sputtered to form a single-layer film (film thickness 1145 · 7A) made of 1.0 film on a glass substrate that has been formed with a light-shielding film, a shirt color photoresist film, and a protective layer maintained at 20 ° (rc). To obtain a color filter. The sheet resistance values of the color filters of the present invention obtained in Examples 15 and 16 and the color filters and filters obtained in Comparative Examples 8 and 9 were obtained. It is obtained by the following method. That is, 67 measurement points are evenly set on the film surface formed on the glass substrate, and the resistance value is obtained using a four-probe resistance meter (MCP-T600) manufactured by Mitsubishi Chemical, and calculated. These average values are calculated and multiplied by a constant value of 4.5424 to obtain the sheet resistance. The film thickness is determined as described below. That is, a two-dimensional micro shape measuring device (ET4000) manufactured by Kosaka Research Institute is used to measure the thickness. The thickness of the conductive film formed on the glass substrate. The measurement is on the glass substrate Set 5 measurement points, mask with force 7 ', tape, and peel off the mask after film formation, and measure the film thickness, and use the average value as the film thickness. Resistivity (Ω · cm) can be determined by It is obtained by multiplying the sheet resistance value obtained by the above-mentioned four-probe method by the film thickness. In addition, the color phosphor films of the present invention obtained from Examples 15 and 16 and the comparative examples 8 and 9 were obtained. The color filter is used to determine the transmittance (% -50 · This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page) ---- ---- ^ ---------. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 521280 A7 B7 V. Description of Invention (48)). That is, a spectrophotometer (U— 2010) And measure the transmittance (%) of the conductive film laminated substrate in the range of 200 ~ 900nm, (Please read the precautions on the back before filling this page) Before forming the film, a light-shielding film and a color photoresist film are formed. The transmittance (%) of the glass substrate (blank) was set to 100%, and the transmittances (%) of 6201011, 5401111, and 4601011111 were calculated. The results are shown in Table 9. Sheet Resistivity, Resistivity, and Transmittance of the conductive film in Table 9 (%) Full film thickness (A) (Ω / □) (Ω · cm) 620nm 540η m 460η m Example 15 1135.5 14. 13 1. 60X 10 '4 90. 89 92. 8 7 97. 7 3 Example 16 1164.6 13. 35 1. 56X 10' 4 91. 08 93. 9 9 98. 6 1 Comparative Example 8 1133. 0 21. 83 2.47X10 " 4 88. 59 90. 7 2 99. 0 7 Comparative Example 9 1145 · 7 18 · 07 2. 07X 10 ~ 4 91 · 56 94. 4 8 98. 9 6 Employees' Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs When the color filters obtained in Examples 15 and 16 were printed to form the first layer of the ITO film, they had the desired performance as a color filter without damage to the color photoresist film. -51- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

521280 A8 B8 C8 D8 VI. Application for Patent Scope 1. A manufacturing method of transparent conductive film laminated substrate has: ⑴Using DC power supply or DC + RF power supply in the environment of inert gas or mixed gas of inert gas and oxygen A step of forming an ITO film by plating a target of indium to tin oxide sintered body in a gas; and (2) using at least one target selected from the group consisting of indium-tin oxide sintered body and indium oxide sintered body, using A step of forming a ΓΓΟ film and / or an indium oxide film on the ITO film formed by the above 0) by applying sputtering in a non-reactive gas ambient gas to a DC power source, an RF power source, or a RF power source. 2. The manufacturing method of the transparent conductive film laminated substrate according to item 1 of the patent application range, wherein the power supply in step (1) is a DC power supply, and the power supply in step (2) is an RF power supply. 3. The manufacturing method of the transparent conductive film laminated substrate of item 2 of the Rushen β patent, wherein the sputtering in step (1) is performed in a mixed gas of inert gas and oxygen, and (2) The sputtering of the step is performed in an inert gas ambient gas. 4. The manufacturing method of the transparent conductive film laminated substrate according to item 丨 of the patent application, wherein the power supply in step (1) is set to a DC power supply, and the power supply in step (2) is set to a DC power supply. 5. The manufacturing method of the transparent conductive film laminated substrate according to item 4 of the patent application, wherein the sputtering in step (1) is performed in a mixed gas of inert gas and oxygen, and the sputtering in step (2) is performed. The plating is performed in an inert gas ambient gas. 6. The method for manufacturing a transparent conductive film laminated substrate according to the first patent application scope, wherein the target used in step (2) is an indium-tin oxide sintered body. 52 This paper size applies to China National Standards (CNS) A4 (210X 297 mm) Ί; P Please read the notes on the back before filling this page). Order. 521280 A8 B8 C8 D8 VI. Patent Application Scope 7 · For example, the method for manufacturing a transparent conductive film laminated substrate according to item 1 of the patent scope, wherein the substrate temperature of the sputtering process in steps (1) and (2) is less than 300 ° C. 8. The manufacturing method of the transparent conductive film laminated substrate according to item 7 of the patent application, wherein the substrate temperature of the sputtering process in step (1) and step (2) is 140 ° C to 250 ° C. m (Please read the precautions on the back before filling out this page) 9 · A method for manufacturing a transparent conductive film laminated substrate, which has: (1) a target for sintering indium-tin oxide using DC power or DC + RF power The step of forming a first layer of ITO film on a substrate by sputtering in an inert gas or a mixed gas of inert gas and oxygen ambient gas; (2) using a DC power source or a DC + RF power source to place the above target in an inactive state A step of forming a second layer of ITO film on the first layer by sputtering in a mixed gas of ambient gas and oxygen; and (3) using a DC power source or a DC + RF power source to place the target in an inactive gas or inactive state A step of forming a third layer of ITO film on the second layer by sputtering in a mixed gas of gas and oxygen in an ambient gas. • Line · 10 · A method for manufacturing a color filter, which is a method for manufacturing a filter in which a light-shielding film, a color photoresist film, and at least two conductive films are sequentially formed on a transparent substrate. Contains: (1) the step of forming an IT0 film using a DC power supply or a DC + RF power supply in the environment of an inert gas or a mixed gas of an inactive gas and oxygen, and a target of a sintered body of indium-tin oxide ; And (2) Use at least one dry seed selected from the group consisting of indium-tin oxide sintered body and indium oxide sintered body, using DC power, RF power or DC + 53 A8 B8 C8 ^ _______ ^ _ Please Patent booth " --- f Please read the precautions on the back before filling in this page) Power supply and sputtering in an inert gas ambient gas to form an IT0 film on the IT0 film formed by the top (1) And / or the step of oxidizing the wedding film. u. The manufacturing method of the color filter according to the scope of the patent application No. 1G, wherein the power supply of step (1) is set to Dc power supply, and the power supply of step (1) is set to power supply. 12. The method for manufacturing a color filter according to item u of the application, wherein the sputtering in step (1) is performed in a mixed gas of inert gas and oxygen, and the sputtering in step (2) is performed. Performed in an inert gas environment. 13. The method for manufacturing a color filter according to item 1 of the scope of patent application, wherein the power supply in step (!) Is set to a DC power supply, and the power supply in step (2) is set to a dc power supply. 14. The method for manufacturing a color filter according to item 13 of the scope of patent application, wherein the sputtering in step (1) is performed in a mixed gas of inert gas and oxygen, and the sputtering in step (2) The plating is performed in an inert gas ambient gas. 15. The method for manufacturing a color filter as described in claim 10, wherein the target used in step (2) is an indium-tin oxide sintered body. 16. The manufacturing method of the transparent conductive film laminated substrate according to item 10 of the patent application, the substrate temperature of the sputtering process in step (1) and step (2) is 140 ° C ~ 250 ° C. 17. A method for manufacturing a color filter, which is a method for manufacturing a filter in which a light-shielding film, a color photoresist film, and at least three conductive films are sequentially formed on a transparent substrate, wherein the conductive film forming step includes: ( 1) Using a DC power supply or a DC + RF power supply to sputter the target of indium-tin oxide sintered in an inert gas or a mixed gas of inert gas and oxygen to form a first layer of ITO film on the substrate Steps: 54 This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 521280 A8 B8 C8 D8 m 6. Application scope of patents, (2) Use DC power or DC + RF power to place the above target in inert gas A step of forming a second layer of ITO film on the first layer by sputtering in a mixed gas of ambient gas and oxygen; and (3) using a DC power source or a DC + RF power source to place the above target in an inactive gas or inactive gas And a step of forming a third layer of ITO film on the second layer by sputtering in a mixed gas of oxygen and oxygen in an ambient gas. (Please read the precautions on the back before filling this page) Order. T 55: Line 丨 This paper size applies to China National Standard (CNS) A4 (210X297 mm)