JP2001121641A - Transparent conductive laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive laminate obtained by forming a transparent conductive film of which the resistance value is reduced immediately after formation on a polymeric substrate and capable of being reduced in its resistance value by applying a stimulus such as heat or the like to the film and a method for producing the same. SOLUTION: In a transparent conductive laminate wherein a transparent conductive film based on indium (In), tin (Sn), Zinc (Zn) and oxygen (O) is formed on a polymeric substrate, the concentration of an Sn atom to the total concentration of In and Sn atoms is 0.01-0.1 and the concentration of a Zn atom to the total concentration of In and Zn atoms is 0.01-0.1 and a ratio of the concentration of the Zn atom to the total concentration of the Sn and Zn atoms is 0-below 0.3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive laminate containing a small amount of zinc and having a reduced resistance value. The present invention relates to a transparent conductive laminate provided with a transparent conductive film capable of lowering resistance.

[0002]

2. Description of the Related Art A transparent conductive film having a high visible light transmittance and low electrical properties is indispensable for an electrode portion of various display elements or thin film solar cells. In addition, with the rapid miniaturization and weight reduction of portable mobile terminals in recent years, further lightweight members are required for transparent electrode substrates. for that reason,
As a substrate material, a film containing In-Sn-O as a main component (hereinafter referred to as I) is used for a transparent polymer substrate material which is lighter than glass.
A transparent conductive film having a laminated structure (to be referred to as a TO film) is being used.

On the other hand, as a new development of transparent conductive materials,
JP-A-6-318406 and JP-A-7-23521
No. 9 proposes a film containing In-Zn-O as a main component (hereinafter referred to as an IZO film). The IZO film, unlike the ITO film, is difficult to be crystallized, and therefore has been developed for applications requiring a relatively high temperature.

[0004] A polymer substrate has poor heat resistance and cannot be applied to a high-temperature process exceeding 200 ° C as used for glass. Therefore, it is very difficult to form an ITO film having a reduced resistance immediately after film formation.

In general, it is said that the structure and electrical characteristics of an ITO film formed by DC magnetron sputtering strongly depend on the film formation temperature. In terms of the structure, in film formation performed while keeping the substrate temperature at room temperature, A film in a state where the crystalline part and the amorphous part are mixed or in an amorphous state is formed. The electrical characteristics of the film formed at a low temperature do not decrease remarkably immediately after the film formation, and generally show a specific resistance of 5 to 7 × 10 ⁻⁴ Ω · cm. On the other hand, IZ
The O film has an amorphous structure immediately after its formation, and has a relatively low resistance value. However, the specific resistance does not change even if a certain stimulus such as heat is applied to the film immediately after the film formation, which is not sufficient for forming a further low-resistance film.

For this reason, various materials have been selected, and even today, there is an insatiable search.

[0007]

In the formation of a transparent conductive film on a polymer substrate, since the softening point temperature of the polymer substrate is generally lower than 200 ° C., the polymer substrate cannot be heated to such a temperature or higher. As in the case of forming a transparent conductive film on glass, a high substrate temperature condition such as 200 to 400 ° C. cannot be used. Further, since the rigidity of the polymer substrate against bending is smaller than that of the glass substrate, a transparent conductive film can be formed on the polymer substrate only up to about 3000 °. If the thickness of the transparent conductive film is made thicker than this, the polymer substrate may be warped (curled) due to the stress of the transparent conductive film, or fine scratches may occur in the transparent conductive film. Sometimes. For this reason, it is necessary to suppress the film thickness to about 3000 ° at the maximum. That is, there is a limit to reducing the resistance value due to the increase in the film thickness on the polymer substrate, and reducing the specific resistance is an essential requirement to realize a low-resistance transparent conductive film on the polymer substrate.

In the case where a transparent conductive film is to be formed using ITO, a high-temperature process exceeding 200 ° C. can form a film having a reduced resistance immediately after the film formation. When a molecular substrate is used, it cannot be denied that the specific resistance of the ITO film immediately after film formation is slightly higher than that of glass.

Accordingly, the present invention provides a transparent conductive film having a reduced resistance value immediately after film formation on a polymer substrate, and further applying a stimulus such as heat to the transparent film to reduce the resistance value. An object of the present invention is to provide a conductive laminate and a method for manufacturing the same.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the composition of a transparent conductive film formed at a substrate temperature of about room temperature, and found that the composition is In-Sn-Zn-O.
By appropriately controlling the Sn concentration and Zn concentration of the system material,
The resistance value of the formed transparent conductive film can be reduced immediately after film formation,
It has further been found that the resistance can be reduced by giving a suitable stimulus, for example heat. This is based on the following means.

In which the Sn concentration and the Zn concentration are appropriately controlled,
When a thin film of -Sn-Zn-O is formed, an amorphous structure is shown immediately after the film is formed. Then, the Zn formed by the low temperature process
In an In—Sn—O film having no, the specific resistance immediately after film formation is slightly higher. However, the heat treatment can significantly reduce the resistance value. On the other hand, in the case of an In—Zn—O film having no Sn, the specific resistance immediately after film formation can be reduced to some extent. The present inventors have found that by adding appropriate amounts of zinc oxide and tin oxide to indium oxide in order to realize these characteristics mutually, it is possible to reduce the specific resistance immediately after film formation even in an amorphous state. I found it. When a stimulus such as heat is applied to the film, the structure changes from amorphous to crystalline. With this crystallization, S
n enters a lattice point, carriers are generated, and the specific resistance is reduced. On the other hand, when Zn enters the lattice points, it becomes difficult to provide oxygen vacancies to In, and the decrease in resistance value due to the effect of Zn is slightly hindered. Therefore, although the reduction in resistance after heat treatment is slightly inferior to that of a single-composition ITO film,
A reduction in resistance immediately after film formation can be realized, and a transparent conductive film having a low resistance can be obtained even after heat treatment. In that sense, it can be considered that the function of the transparent conductive film is enhanced by the composite of In ₂ O ₃ , ZnO, and SnO ₂ .

That is, the present invention preferably comprises In-Sn-Z
A transparent conductive laminate in which a transparent conductive film is formed on a polymer substrate by a DC magnetron sputtering method using a sintering target containing n-O as a main component, wherein Sn is based on the total atomic concentration of In and Sn. The atomic concentration falls within the range of 0.01 to 0.1, and Zn relative to the total atomic concentration of In and Zn
Is in the range of 0.01 to 0.1, and Sn
And a ratio of the atomic concentration of Zn to the total atomic concentration of Zn and Zn is greater than 0 and less than 0.3. The specific resistance immediately after the formation of the film is 3.5 × 10 ^{−4 to} 5.0 × 10 ⁻⁴ Ω · cm, and at a temperature equal to or lower than the softening point temperature of the polymer substrate,
The specific resistance of the film is set to 2.0 × 10 ^{−4 to} 3.5 by heat-treating the film for 10 minutes to 300 minutes.
It is characterized in that it can be converted to × 10 ⁻⁴ Ω · cm.
At this time, the transparent conductive film has a thickness of 100 to 2800 °, and the base polymer substrate has a thickness of 0.01 to 0.4 mm.

[0013]

Next, embodiments of the present invention will be sequentially described. The transparent conductive laminate of the present invention is obtained by forming a transparent conductive film on a polymer substrate.

The transparent conductive film according to the present invention comprises indium oxide as a main component, tin oxide and zinc oxide added, and the ratio of the atomic concentration of Sn to the sum of the atomic concentrations of In and Sn is 0.01 to 0.01. 0.1 and In and Zn
The ratio of the atomic concentration of Zn to the sum of the atomic concentrations of
And the ratio of the atomic concentration of Zn to the sum of the atomic concentrations of Sn and Zn falls within the range of more than 0 and less than 0.30, and the range of 0.10 to 0.25. It is desirable to enter. If the Zn concentration relative to the sum of the atomic concentrations of Sn and Zn is lower than 0.01, the specific resistance immediately after the film formation does not decrease so much. On the other hand, from 0.3, Sn and Z
When the concentration of Zn with respect to the sum of the atomic concentrations of n is low,
Although the specific resistance immediately after the film formation is reduced, the specific resistance increases after the heat treatment.

The polymer substrate used in the present invention comprises a single component such as a polyester polymer, a polyolefin polymer, a polyester such as polyethylene terephthalate or polyethylene 2,6-naphthalate, a polycarbonate, a polyether sulfone, or a polyarylate. In order to provide a polymer or an optical function or a thermodynamic function, a polymer obtained by copolymerizing a second or third component with these polymers can be used. In particular, polycarbonates having a bisphenol component and good transparency are suitable for optical applications. Examples of such bisphenol components include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z),
1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-
4-hydroxyphenyl) fluorene. These may be used in combination of two or more. That is, such a polycarbonate may be a copolymerized polycarbonate or a blend. Further, a polymer obtained by blending a plurality of polymer materials to exhibit a new function can also be used. Further, a multi-layer coextruded polymer film can be used.

The thickness of the polymer substrate is from 0.01 to
0.4 mm can be used, but 0.1 to
About 0.2 mm is desirable from the viewpoint of visibility for optical applications such as liquid crystal.

Further, the polymer substrate preferably has excellent optical isotropy, and preferably has a retardation of 20 nm or less, preferably 10 nm or less.

The polymer substrate is provided on one or both sides of the polymer substrate in order to improve the adhesion to the formed transparent conductive film, the durability of the polymer substrate, or the gas barrier capability of the polymer substrate. May have at least one coating layer. This coating layer is made of an inorganic or organic substance or a composite material thereof, and preferably has a thickness of 0.01 to 20 μm. More desirably, it is desirable to be suppressed to about 10 mm. For forming the coating layer, an application method using a coater, a spray method, a spin coating method, an in-line coating method, and the like are often used, but are not limited thereto. Physic, such as sputtering and vapor deposition,
al Vapor Deposition (hereinafter referred to as PV
D), Chemical Vapor Depositi
On (hereinafter referred to as CVD) may be used. As the coating layer, a resin component such as an acrylic resin, a urethane resin, a UV curable resin, or an epoxy resin, or a mixture of these with inorganic particles such as alumina, silica, and mica may be used. Alternatively, a polymer substrate may be provided with the function of a coating layer by co-extrusion of two or more layers. In the PVD and CVD methods, magnesium oxide,
Oxides such as aluminum oxide, silicon oxide, calcium oxide, barium oxide, tin oxide, indium oxide, tantalum oxide, titanium oxide, and zinc oxide; nitrides such as silicon nitride, titanium nitride, and tantalum nitride; and magnesium fluoride And fluorides such as calcium fluoride can be used alone or as a mixture. It is desirable that the polymer substrate having such a coating layer has a low retardation and a high transmittance as optical characteristics.

In the present invention, the transparent conductive film is formed by a DC magnetron sputtering method, an RF magnetron sputtering method, an ion plating method, a vacuum deposition method, a pulse laser deposition method, or a combination of these methods. However, a DC magnetron sputtering method is desirable in view of industrial production in which a transparent conductive film having a uniform thickness is formed on a large area.

The target used for sputtering is In.
Although it is desirable to use a sintered target mainly containing -Sn-Zn-O, an alloy target mainly containing In-Sn-Zn may be used.

In the present invention, when the transparent conductive film is formed by a sputtering method, the pressure in the vacuum chamber for forming the transparent conductive film is once reduced to 1.3 × 10 ⁻⁴ Pa or less, and then inert. It can be formed by a manufacturing method in which gas and oxygen are introduced. It is feared that once the pressure in the vacuum chamber for forming the transparent conductive film is 1.3 × 10 ⁻⁴ Pa or less, the pressure remains in the vacuum chamber and affects the characteristics of the transparent conductive film. This is desirable because the influence of molecular species can be reduced. More preferably, the pressure is 4 × 10 ⁻⁵ Pa or less, further preferably 2 × 10 ⁻⁵ Pa or less.

The inert gas introduced next is H
It is said that e, Ne, Ar, Kr, and Xe can be used, and it is said that an inert gas having a larger atomic weight causes less damage to a film to be formed and lowers specific resistance. Is desirable. In order to adjust the concentration of oxygen taken into the film, oxygen in the order of 1 × 10 ^{−4 to} 1.3 × 10 ⁻² Pa in terms of partial pressure may be added to the inert gas. Further, in addition to oxygen, O ₃ , N ₂ , N ₂ O, N
H ₃ or the like can be used.

In the present invention, a transparent conductive film is formed.
The partial pressure of water in the vacuum chamber is 1.3 × 10 ^-FourPa or less, then
Formed by a production method that introduces inert gas and oxygen.
Can be The water partial pressure is more desirably 4 × 1
0^-FivePa or less, more preferably 2 × 10^-FiveBelow Pa
Control the water pressure.

When determining the water pressure in the present invention, a differential exhaust type in-process monitor may be used. Alternatively, a quadrupole mass spectrometer that has a wide dynamic range and can measure even under a pressure of about 0.1 Pa may be used. In general, at a degree of vacuum of about 1 × 10 ⁻⁵ Pa, water forms the pressure. Therefore, the value measured by the vacuum gauge may be considered as the water pressure as it is.

In the present invention, since a polymer substrate is used, the substrate temperature cannot be raised above the softening point temperature of the polymer substrate. Therefore, in order to form a transparent conductive film, the temperature of the polymer substrate needs to be from about room temperature to a softening point temperature or lower. In the case of polyethylene terephthalate, which is a typical polymer substrate, the softening point temperature is about 80 ° C. when no special treatment is performed.
It is desirable to form the conductive layer while maintaining the temperature at 0 ° C. or lower. More desirably, the conductive layer is formed at room temperature.

The transparent conductive film formed according to the present invention has a specific resistance of 3.5 × 10 ^{-4 to} 5.0 × 10 ^-4 Ω.
Shows the specific resistance in cm.

When such a film is subjected to a heat treatment at a temperature not exceeding the softening point temperature of the polymer substrate, the resistance value can be reduced as compared with immediately after the film formation. The heat treatment time is desirably performed in a short time in view of industrial production, and is 10 minutes or more and 300 minutes or less. More preferably, it is in the range of 10 to 240 minutes, and still more preferably, it is 10 to 120 minutes. If the heat treatment time is less than 10 minutes, the heating of the transparent conductive laminate becomes insufficient. Further, the heat treatment for longer than 300 minutes is a time for which the stability of the polymer with respect to the temperature can be reliably ensured. For example, if a thermally stable polymer substrate is used, it may be as long as 1000 minutes. No problem. However, considering the actual process, it is desirable that the time be within about 300 minutes. By performing the heat treatment, the specific resistance of the film can be converted to 2.0 × 10 ^{−4 to} 3.5 × 10 ⁻⁴ Ω · cm. The same effect can be obtained by giving a stimulus instead of the heat treatment to the transparent conductive film. For example, the same effect as the heat treatment can be obtained by irradiating a pulse laser or irradiating an electron beam. However, considering the capital investment, heat treatment is considered to be the most efficient. The atmosphere in which the heat treatment is performed may be either air or vacuum. Also,
Heat treatment in an inert gas atmosphere may be used. However, it is efficient and preferred to carry out in air.

The thickness of the transparent conductive film depends on the application. However, since the flexibility is deteriorated, it is not desirable to have a transparent conductive film of 3000 ° or more. Also, 10
When the thickness is 0 ° or less, the function as a transparent conductive film is significantly deteriorated. Therefore, the thickness of the transparent conductive film of the present invention is 100
It is desirably set to ~ 2800 °.

The surface resistance of the transparent conductive film in the present invention was measured using Loresta MPMCP-T350 manufactured by Mitsubishi Chemical Corporation. The film thickness of the transparent conductive film was obtained by measuring the level difference of the film formed on glass using Dektak manufactured by Sloan Corporation, calculating the sputter rate, and calculating the reverse.

In the present invention, not only the resistance value but also the total light transmittance, which is one of the other basic physical quantities of the transparent conductive film, and the X-ray diffraction which gives knowledge on the structure of the film are examined. I am doing it. Total light transmittance is NIPP
The measurement was carried out without separating the polymer substrate and the transparent conductive film using 300A manufactured by ON DENSHOKU. The X-ray diffraction was measured by using RU-300 manufactured by Rigaku Denki Co., Ltd. in an optical arrangement by a concentrated method.

The structural feature is that the result is a mixture of amorphous and crystalline immediately after film formation.
When the heat treatment for 00 minutes is performed at a temperature lower than the softening point temperature of the polymer substrate, the film can be converted into a crystalline film.

The total light transmittance of the transparent conductive laminate of the present invention is good and is in the range of 70 to 88% immediately after film formation by the above-mentioned film forming method. 10-30 at a temperature not exceeding the glass transition temperature
When the heat treatment is performed for 0 minutes, the total light transmittance is further increased and can be converted to 80 to 89%.

[0033]

The present invention is not limited to the following examples.

Example 1 The back pressure of the vacuum chamber was set to 1.3 × 10
^-5 Pa, oxygen was introduced as a reaction gas, and Ar was introduced as an inert gas, and the total pressure was set to 0.4 Pa. The water pressure before the introduction of the inert gas, measured by a quadrupole mass spectrometer, was almost equal to the back pressure of the vacuum chamber. The oxygen partial pressure was 2.7 × 10 ⁻³ Pa.

A 130 nm thick transparent conductive film is formed on a polycarbonate substrate at a substrate temperature of 20 ° C. by a DC magnetron sputtering method at a power density of 1 W / cm ^{2 on} a sintered target made of In—Sn—Zn—O. did. The ratio of the atomic concentration of Zn to the total atomic concentration of In and Zn was 0.022, and the ratio of the atomic concentration of Sn to the total atomic concentration of In and Sn was 0.092. Sn
The ratio of the atomic concentration of Zn to the total of the atomic concentrations of Zn and Zn was 0.19.

The specific resistance immediately after the formation of the film is determined by a four-terminal resistance.
5.0 × 10 ^-FourΩ · cm
Was. The total light transmittance was 81%.

The film was subjected to a heat treatment at 130 ° C., which is a temperature lower than the softening point temperature of polycarbonate, for 30 minutes, and the specific resistance was measured by a four-terminal resistance meter to be 2.3 × 10 ⁻⁴ Ω ·
cm. The total light transmittance was 87%. When the heat treatment time was 240 minutes, the specific resistance and the total light transmittance were the same.

In Examples and Comparative Examples of the present invention, the ratio of Sn atom concentration to the sum of In atom concentration and Sn atom concentration,
Table 1 shows the ratio of the Zn atom concentration to the sum of the In atom concentration and the Zn atom concentration, and the ratio of the Zn atom concentration to the sum of the Sn atom concentration and the Zn atom concentration. Table 1 also shows the specific resistance and total light transmittance before and after the heat treatment.

Example 2 The back pressure of the vacuum chamber was the same as in Example 1, oxygen was introduced as a reaction gas, and Ar was introduced as an inert gas to make the total pressure 0.4 Pa. The water pressure before the introduction of the inert gas measured by the quadrupole mass spectrometer was almost equal to the back pressure of the vacuum chamber. The oxygen partial pressure is 3.
It was 5 × 10 ⁻³ Pa.

A 130 nm thick transparent conductive film was formed on a polycarbonate substrate at a substrate temperature of 20 ° C. by a DC magnetron sputtering method at a power density of 1 W / cm ^{2 on} a sintered target made of In—Sn—Zn—O. did. The ratio of the atomic concentration of Zn to the total atomic concentration of In and Zn was 0.018, and the ratio of the atomic concentration of Sn to the total atomic concentration of In and Sn was 0.099. Sn
The ratio of the atomic concentration of Zn to the total of the atomic concentrations of Zn and Zn was 0.14.

The specific resistance immediately after the formation of the film is defined as a four-terminal resistance.
4.3 × 10 ^-FourΩ · cm
Was. The total light transmittance was 80%.

The film was subjected to a heat treatment at 130 ° C., which is a temperature lower than the softening point temperature of polycarbonate, for 30 minutes, and the specific resistance was measured with a four-terminal resistance meter to be 2.5 × 10 ⁻⁴ Ω ·
cm. The total light transmittance was 85%. When the heat treatment time was 240 minutes, the specific resistance and the total light transmittance were the same.

Example 3 The back pressure of the vacuum chamber was the same as in Example 1, oxygen was introduced as a reaction gas, and Ar was introduced as an inert gas to make the total pressure 0.4 Pa. The water pressure before the introduction of the inert gas measured by the quadrupole mass spectrometer was almost equal to the back pressure of the vacuum chamber. The oxygen partial pressure is 2.
It was 7 × 10 ⁻³ Pa.

On a sintered target composed of In-Sn-Zn-O, at a power density of 1 W / cm ² , a DC magnetron sputtering method was applied to a polycarbonate substrate having a 3 mm organic coating layer formed on both sides at a substrate temperature of 20 ° C. 1
A transparent conductive film having a thickness of 30 nm was formed. The ratio of the atomic concentration of Zn to the total atomic concentration of In and Zn is 0.022.
And the ratio of the atomic concentration of Sn to the total atomic concentration of In and Sn was 0.092. The ratio of the atomic concentration of Zn to the total of the atomic concentrations of Sn and Zn was 0.19.

The specific resistance immediately after the formation of the film was determined as a four-terminal resistance.
4.9 × 10 ^-FourΩ · cm
Was. The total light transmittance was 84%.

The film was subjected to a heat treatment at 130 ° C., which is lower than the softening point temperature of polycarbonate, for 30 minutes, and the specific resistance was measured by a four-terminal resistance meter to be 2.4 × 10 ⁻⁴ Ω ·.
cm. The total light transmittance was 87%. When the heat treatment time was 240 minutes, the specific resistance and the total light transmittance were the same.

Comparative Example 1 The back pressure of the vacuum chamber was the same as in Example 1, oxygen was introduced as a reaction gas, and Ar was introduced as an inert gas to make the total pressure 0.4 Pa. The water pressure measured with a quadrupole mass spectrometer before the introduction of the reaction gas and the inert gas was almost equal to the back pressure of the vacuum chamber. The oxygen partial pressure was 2.7 × 10 ⁻³ Pa.

A transparent conductive film having a thickness of 130 nm was formed on a polycarbonate substrate at a substrate temperature of 20 ° C. by a DC magnetron sputtering method at a power density of 1 W / cm ^{2 on} a sintered target made of In—Sn—Zn—O. did. The ratio of the atomic concentration of Zn to the total atomic concentration of In and Zn was 0.042, and the ratio of the atomic concentration of Sn to the total atomic concentration of In and Sn was 0.073. Sn
The ratio of the atomic concentration of Zn to the sum of the atomic concentrations of Zn and Zn was 0.37.

The specific resistance immediately after the formation of the film is defined as a four-terminal resistance.
3.4 × 10 ^-FourΩ · cm
Was. The total light transmittance was 84%.

The film was subjected to a heat treatment at 130 ° C., which is lower than the softening point temperature of polycarbonate, for 30 minutes, and the specific resistance was measured with a four-terminal resistance meter to find that it was 5.1 × 10 ⁻⁴ Ω ·.
cm. The total light transmittance was 86%. When the heat treatment time was 240 minutes, the specific resistance and the total light transmittance were the same.

Although the specific resistance immediately after the film formation is slightly improved, the specific resistance increases with the heat treatment, and it is hard to say that the film is a low specific resistance film.

Comparative Example 2 The back pressure of the vacuum chamber was the same as in Example 1, oxygen was introduced as a reaction gas, and Ar was introduced as an inert gas to make the total pressure 0.4 Pa. The water pressure measured with a quadrupole mass spectrometer before the introduction of the reaction gas and the inert gas was almost equal to the back pressure of the vacuum chamber. The oxygen partial pressure was 3.3 × 10 ⁻³ Pa.

A 130 nm-thick transparent conductive film was formed on a polycarbonate substrate at a substrate temperature of 20 ° C. by a DC magnetron sputtering method at a power density of 1 W / cm ^{2 on} a sintered target made of In—Sn—Zn—O. did. No zinc oxide was added. The ratio of the atomic concentration of Sn to the total atomic concentration of In and Sn was 0.093.

The specific resistance immediately after the formation of the film is defined as a four-terminal resistance.
5.6 × 10 ^-FourΩ · cm
Was. The total light transmittance was 80%.

The film was subjected to a heat treatment at 130 ° C., which is lower than the softening point temperature of polycarbonate, for 30 minutes, and the specific resistance was measured with a four-terminal resistance meter to be 2.0 × 10 ⁻⁴ Ω ·
cm. The total light transmittance was 86%. When the heat treatment time was 240 minutes, the specific resistance and the total light transmittance were the same.

Although the specific resistance is significantly reduced by the heat treatment, the specific resistance immediately after film formation is high.

[0057]

[Table 1]

[0058]

As described above, according to the present invention,
In a transparent conductive laminate formed on a polymer substrate by a low-temperature process, a transparent conductive laminate having a low resistance immediately after film formation and having a lower resistance after heat treatment can be provided.

Continued on the front page F term (reference) 4F100 AA40B AB18B AB21B AB40B AK01A AK45 AR00B BA02 GB90 JA20A JA20B JG01B JG04B JM02B JN01B YY00B 5G307 FA02 FB01 FC10 5G323 BA01 BA02 BB05 BC03

Claims (4)

[Claims] 1. A transparent conductive laminate comprising a transparent conductive film mainly composed of indium (In), tin (Sn), zinc (Zn) and oxygen atoms (O) formed on a polymer substrate. , The atomic concentration of Sn with respect to the total atomic concentration of In and Sn is in the range of 0.01 to 0.1, the atomic concentration of Zn with respect to the total atomic concentration of In and Zn is in the range of 0.01 to 0.1, And Zn with respect to the total atomic concentration of Sn and Zn
Wherein the ratio of the atomic concentration of the transparent conductive laminate is greater than 0 and less than 0.30. 2. The transparent conductive film has a specific resistance of 2.0 × 10 ⁻⁴ or ^less .
The transparent conductive laminate according to claim 1, wherein the transparent conductive laminate has a thickness of 3.5 × 10 ⁻⁴ Ω · cm. 3. The transparent conductive film has a thickness of 100 to 2800 °.
The transparent conductive laminate according to claim 1, wherein: 4. The polymer substrate has a thickness of 0.01 to 0.4 m.
m. The transparent conductive laminate according to claim 1, wherein m is m.