JP2001291445A - Method of producing patterned electrode substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode substrate having a low specific resistance, capable of being patterned and converted into a transparent conductive film having the low specific resistance with heat treatment after an etching process. SOLUTION: In producing processes for the electrode substrate including a patterning process for the transparent conductive film after etching treatment for a transparent conductive laminate, the transparent conductive film is crystallized after an etching treatment, instead of before the etching treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to indium (I)
n), an electrode substrate having a transparent conductive film containing tin (Sn) and oxygen atoms (O) as main components, and in particular, In, Sn and O are formed on a substrate (polymer substrate) made of a polymer film.
The present invention relates to a low-resistance electrode substrate which is provided with a transparent conductive film mainly composed of, and has a reduced resistance value after etching for patterning, and a method for manufacturing the same.

[0002] In the present specification, "patterning"
Means "giving a pattern to the surface of the transparent conductive film", and the work for that is called "etching".

[0003]

2. Description of the Related Art A transparent conductive film having high visible light transmittance and low resistance is used for various display elements such as a liquid crystal display element (LCD) and an electroluminescence display element (EL) or an electrode portion of a thin film solar cell. necessary.

Further, with the rapid miniaturization and weight reduction of portable mobile terminals in recent years, lighter members are also required for electrode substrates.

[0005] Therefore, as a substrate material, a transparent polymer material such as a polymer film (also referred to as a polymer substrate) which is lighter than glass and a transparent conductive film containing In, Sn and O as main components are used. (Hereinafter, also referred to as an ITO film) is being used.

When a color display element is to be manufactured using an ITO film formed on a polymer substrate, an ITO film is required.
The surface resistance of the film is desired to be about 20Ω / □.

In order to form an ITO film on a glass and / or polymer substrate, DC magnetron sputtering, RF magnetron sputtering, vacuum deposition, ion plating, and the like are used. In particular, DC magnetron sputtering is effective for forming a transparent conductive film in which various physical properties such as a film thickness in a width direction and a longitudinal direction are stabilized for a large area.

An ITO film laminated on a polymer substrate generally has a problem that its surface resistance is higher than that of an ITO film laminated on a glass substrate.

[0009] This is mainly due to two factors. One is that, because the process temperature is lower than that of a film formation process on a glass substrate, crystal growth cannot be performed sufficiently and the film is amorphous. The other is the limitation of the film thickness due to the rigidity of the polymer substrate, that is, if the ITO film is made thicker, the warpage of the substrate becomes extremely large or cracks occur in the ITO film as described later. The constraint.

For these reasons, IT on a polymer substrate
The O film has a specific resistance less than 5.0 × 10 ⁻⁴ Ω · cm, and it is difficult to form a film having a surface resistance value lower than 40 Ω / □.

As a measure for reducing the specific resistance of the transparent conductive film, it is necessary to obtain a crystalline ITO film. However, using a crystalline ITO film has been found to cause new problems in patterning,
It is not a fundamental solution.

That is, in order to form an element using the transparent conductive laminate, it is necessary to pattern the transparent conductive film in the transparent conductive laminate to obtain a desired pattern, and etching for patterning is performed using an acid. However, the concentration or temperature of the acid strongly depends on the state of the transparent conductive film.

In order to etch a crystalline ITO film, it is often necessary to use hydrochloric acid having a concentration of about 30% by weight or more as an etchant.
When such a high-concentration etchant is used, even a polymer substrate excellent in chemical resistance may be damaged such as whitening of the substrate.

That is, if the ITO film is made amorphous, the surface resistance becomes high.
If the film is made crystalline, the possibility that the polymer substrate is damaged during the etching process is increased.

On the other hand, since the current amorphous ITO film can be etched with a weak acid and the polymer substrate is hardly damaged, it is unacceptable to lose its merit by crystallization on purpose. .

That is, in order to realize a low resistance value, it is necessary to make the ITO film crystalline, and to make patterning with a weak acid easy, it is necessary to make the ITO film amorphous. Due to trade-offs, means for realizing both a low resistance value and easy patterning with a weak acid to prevent the polymer substrate from being damaged has not been known for an electrode substrate using a polymer substrate.

[0017]

In view of the above situation, there has been a demand for a transparent conductive film which does not damage the polymer substrate in the etching step and has a low resistance when used.

[0018]

Means for Solving the Problems The present inventors have paid attention to the fact that the transparent conductive film before the etching step has an excellent etching characteristic if it is amorphous, and the transparent conductive film after the etching step is used. It was considered that the resistance value could be reduced and a suitable electrode substrate could be obtained by conversion to crystalline in the heat treatment step in the subsequent liquid crystal cell formation process.

The inventors of the present invention have an amorphous structure having excellent etching characteristics before etching, and perform appropriate heat treatment after etching to crystallize the transparent conductive film, which results in a difference between the etching characteristics and the resistance value. Focusing on the fact that it is very important in avoiding the trade-off relationship, the present inventors have conducted intensive studies on the crystallization process of the transparent conductive film. As a result, they succeeded in producing an electrode substrate on which a transparent conductive film capable of realizing crystallization at an extremely limited temperature range was formed.

That is, the present invention is as follows. 1. In a method for manufacturing an electrode substrate, comprising a step of etching a transparent conductive laminate having a transparent conductive film formed on a polymer substrate and patterning the transparent conductive film, the transparent conductive film is not crystallized before the etching process. And a method of manufacturing a patterned electrode substrate, wherein the transparent conductive film is crystallized after the etching process.

2. 2. The method for manufacturing an electrode substrate according to the above item 1, further comprising a step of performing a heat treatment at 130 to 200 ° C. after the step of patterning the transparent conductive film by etching.

3. A 3.5 to 20% by weight aqueous solution of an etchant component containing hydrogen chloride as an etchant component is used as an etchant, and the etching process is performed while maintaining the etchant at a temperature of 30 ° C. or lower. 3. The method for manufacturing an electrode substrate according to 1 or 2 above.

4. 0.75 for 1 part by weight of hydrogen chloride
(1) wherein ferric chloride is contained as an etchant component in an amount of up to 1.25 parts by weight.
The method for producing an electrode substrate according to any one of the above.

5. Heat treatment at 130-200 ° C for 120
The method for producing an electrode substrate according to any one of the above items 2 to 4, wherein the method is carried out for up to 300 minutes.

6. The transparent conductive film is made of indium (I
6. The method for producing an electrode substrate according to any one of the above items 1 to 5, wherein the method is a transparent conductive film containing n), tin (Sn) and oxygen atoms (O) as main components.

7. 7. The method for manufacturing an electrode substrate according to any one of the above items 1 to 6, wherein a specific resistance of the transparent conductive film before the etching treatment is 4.0 to 10.0 × 10 ⁻⁴ Ω · cm.

8. 8. The method for manufacturing an electrode substrate according to any one of the above items 1 to 7, wherein the resistivity of the transparent conductive film after the heat treatment after the etching treatment is 1.0 to 3.5 × 10 ⁻⁴ Ω · cm.

In a desirable mode of the transparent conductive film of the electrode substrate, a conductive material mainly containing indium (In), tin (Sn) and oxygen atom (O) is used, and the specific resistance before etching is 4. 0 to 10.0 × 10 ⁻⁴ Ω · cm. After the etching, the specific resistance is set to 1.
It can be converted to 0 to 3.5 × 10 ⁻⁴ Ω · cm.

In the transparent conductive film formed on the electrode substrate, a group of nitrogen, carbon dioxide, carbon monoxide, water, ammonia, laughing gas, nitrogen dioxide, and methane together with an inert gas and oxygen at the time of film formation. It can be prepared by introducing at least one kind of gas selected in the range of 0.01 to 3% by volume of the inert gas. When introducing as a compound such as carbon dioxide, carbon monoxide, water, ammonia, laughing gas, nitrogen dioxide, methane, etc., the same effect as introducing a light element such as nitrogen, hydrogen, oxygen, carbon alone can be obtained There are many.

[0030]

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

The polymer substrate used in the present invention includes polyester polymers such as polyethylene terephthalate and polyethylene 2,6 naphthalate, polyolefin polymers, polycarbonate, polyether sulfone, and the like.
Use of a single-component polymer such as polyarylate, or a copolymer obtained by copolymerizing a second or third component with these polymers to provide an optical function or a thermodynamic function it can.

In particular, polycarbonates having a bisphenol component and having good transparency are suitable for optical applications.

Examples of the bisphenol component 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 polymers can be used in order to exhibit a new function. Further, a multi-layer coextruded polymer film can be used.

The thickness of the polymer substrate is 0.01 to 0.4 m
m can be used, but 0.1 to 0.2 m
m is desirable from the viewpoint of visibility. Also, 0.01m
After forming on a polymer substrate of about m, it may be bonded to a thick polymer film.

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 side of the polymer substrate 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. Both surfaces may have at least one coating layer.

The 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 preferably, 10
It is desirable that the thickness be suppressed to about μm.

For the formation of the coating layer, a coating method using a coater, a spray method, a spin coating method, an in-line coating method and the like are often used, but not limited thereto.

Further, Ph, such as a sputtering method and a vapor deposition method, may be used.
ysical Vapor Deposition (P
VD), Chemical Vapor Deposi
Tion (CVD) technique 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, the function of the coating layer may be provided by co-extrusion of two or more layers of the polymer substrate.

In the PVD and CVD techniques, magnesium oxide, aluminum oxide, silicon oxide, calcium oxide,
Oxides such as barium oxide, tin oxide, indium oxide, tantalum oxide, titanium oxide, and zinc oxide; nitrides such as aluminum nitride, silicon nitride, titanium nitride, and tantalum nitride; and fluorides such as magnesium fluoride and calcium fluoride Can be used singly or by mixing.

Before the etching step in the present invention, a photo resist film is formed. The photo resist film is fixed by pre-baking before etching. The transparent conductive film according to the present invention is in an amorphous state such that crystallization does not occur when the photo resist film is heat-treated (prebaked) at 90 to 110 ° C. within 60 minutes.

In the etching step according to the present invention, the transparent conductive film is in an amorphous state or in a state in which the transparent conductive film is slightly present. Therefore, an aqueous solution etchant of 30 ° C. or lower can be used for etching.

The etchant components of this etchant include aqua regia, hydrogen halide, phosphoric acid, sulfuric acid, nitric acid, chloric acid, organic acids such as acetic acid and oxalic acid, iodine, ferric chloride (F
eCl ₃ ), combinations of these, and the like.

In particular, a combination of hydrogen halide and iodine and / or hydrogen halide and ferric chloride (FeCl ₃ ) is suitable as an etchant component.

Among them, 3.5 to 3.5 of the etchant component
20% by weight aqueous solution containing halo as an etchant component
Aqueous solutions containing hydrogen genide are preferred as etchants.
New And, together with the hydrogen halide, iodine and / or
Or ferric chloride (FeCl _Three) With the etchant ingredients
It is more preferable that they coexist.

An aqueous solution containing 3.5 to 20% by weight of this etchant component and containing hydrogen halide as an etchant component is used in an amount of 0.75 to 1.25 parts by weight per 1 part by weight of the hydrogen halide. More preferably, ferric chloride is contained as an etchant component.

Of the hydrogen halides, hydrogen chloride is particularly preferred. Also, a small amount of nitric acid or sulfuric acid may be added as an etchant component.

In the present specification, the amounts of “hydrogen halide” (or “hydrogen chloride”) and “ferric chloride” in the etchant can be determined as follows.

The aqueous solution is filtered to remove insolubles. This is designated as Sample 1.

The amount of halogen (or chlorine) (including both those free of ions and those not ionized by ions) contained in Sample 1 is determined. This is defined as a halogen (or chlorine) amount of 1.

The metal dissolved in sample 1 is determined. (This metal component includes, in addition to the iron derived from ferric chloride that has been added, other metals added as necessary and metals that dissolve in the aqueous solution during etching.)

In the case of iron, it is assumed that the metal is trivalent, and in the case of other metals, it is assumed that it has the most stable valence when it is a halide (or chloride). Or chloride), the halogen (or chlorine) amount is defined as halogen (or chlorine) amount 2.

The amount obtained by subtracting the amount of halogen (or chlorine) 2 from the amount of halogen (or chlorine) 1 is defined as the amount of halogen (or chlorine) 3.

The amount of hydrogen halide (or hydrogen chloride) corresponding to the halogen (or chlorine) amount 3 (ie, equimolar) is defined as the “hydrogen halide” (or “hydrogen chloride”) amount according to the present invention.

The amount of ferric chloride corresponding to the amount of iron determined above (ie, equimolar) is defined as the amount of “ferric chloride” according to the present invention.

More specifically, for example, to prepare a hydrogen chloride-containing aqueous solution containing 5% by weight of hydrogen chloride and 5% by weight of ferric chloride, the following method can be used. That is, first, concentrated hydrochloric acid is diluted with pure water to prepare a 10% by weight solution. The etchant obtained by such an operation is
Called 0% by weight etchant.

Then, a saturated ferric chloride solution containing 40% by weight of ferric chloride is diluted with pure water to prepare a 10% by weight solution.

Finally, the two 10% by weight solutions are mixed to prepare a hydrogen chloride-containing aqueous solution containing 5% by weight of hydrogen chloride and 5% by weight of ferric chloride. In this manner, the solution obtained by mixing the two 10% by weight solutions is also 1 solution.
Called 0% by weight etchant.

As described above, in the present specification, “X wt% etchant” means a solution containing the aforementioned etchant component in a total amount of X wt%.

In an aqueous solution etchant containing hydrogen halide as an etchant component, if the content of the etchant component is less than 3.5% by weight, the etching time takes several minutes or more, leading to a decrease in yield. If it exceeds 20% by weight, the etching time is too short, and it is difficult to obtain a desired circuit. The etchant temperature is 30 ° C. to reduce damage to the polymer substrate.
It is desirable to make the following.

After forming a desired circuit, the photo resist is peeled off and heat treatment is performed. At this time, it is also possible to previously form a liquid film for forming a liquid crystal alignment film on the patterned surface, and simultaneously form the liquid crystal alignment film by the above-described heat treatment. Incidentally, a polyimide film is usually used for the liquid crystal alignment film.

The heat treatment is performed at a temperature of 130 to 200 ° C. for 120 minutes.
It is desirable to carry out over 300 minutes. The transparent conductive film in the present invention has a temperature of about 60 to 110 ° C.
A minute heat treatment (pre-bake) does not cause crystallization, but by appropriately controlling the amorphous state, a heat treatment at a temperature of 130 to 200 ° C. for about 120 to 300 minutes may cause crystallization. It is better to be able to realize

If the polymer substrate can withstand temperatures up to about 200 ° C., the heat treatment time can be further reduced. However, in this case, reversible deformation occurs in the polymer substrate, and a crack may be formed in the transparent conductive film due to a difference in thermal expansion coefficient between the polymer substrate and the transparent conductive film converted into crystalline. Therefore, a temperature of 130 to 170C is more desirable.
More preferably, the temperature is 130 to 150 ° C.

As a method for forming the transparent conductive film in the present invention, a PVD method such as a sputtering method, a vapor deposition method, and an ion plating method can be used. However, a sputtering method is desirable in view of an increase in area. In addition, it is desirable to use a magnetron method in a DC method or an AC method as the sputtering method.

The transparent conductive film made of In, Sn, and O can be formed by sputtering using an oxide sintered target containing indium oxide as a base material and containing 5 to 25% by weight of tin oxide. A more desirable concentration of tin oxide is 5 to 15
% By weight. In view of the reduction in resistance, the concentration of tin oxide is desirably 7.5 to 15% by weight.

On the other hand, in order to carry out crystallization particularly smoothly in the above-mentioned temperature range, the concentration of tin oxide is 5 to 10% by weight.
Is desirable. Further, a metal target made of In and Sn can be used. However, it is desirable to use an oxide sintered target from the viewpoint of easy formation of the transparent conductive film. Also, in order to smoothly reduce the resistance value,
A third component may be added.

The above-mentioned concentration of tin oxide in the target substantially coincides with the concentration of tin oxide in the formed conductive film.

It is desirable to use Ar as a process gas used for sputtering. In addition, He, Ne, K
A rare gas such as r or Xe may be used. But,
Ar, which has high cost merit, is optimal. Further, it is preferable to add oxygen in order to supplement oxygen in the formed ITO film.

In forming the ITO film, A
r, oxygen, nitrogen, carbon dioxide, carbon monoxide, water,
At least one of a gas consisting of the group consisting of ammonia, laughing gas, nitrogen dioxide, and methane,
It can be introduced at a volume fraction of 1 to 3% by volume. Hydrogen may be less desirable than it is difficult to handle and requires a special pump for evacuation.

For example, in the case of nitrogen, when incorporated into the transparent conductive film, it contributes to structural relaxation, so that a good amorphous transparent conductive film having a slightly reduced resistance value can be formed. In the case of water as well, structural relaxation occurs when protons are introduced into the membrane. In addition, if water is used, hydrogen is generated by dissociation in the plasma, so that the method is more efficient and safer than the method of introducing hydrogen gas. However, when these gases are introduced in excess of 3% by volume with respect to Ar,
The features of these components are surfaced, which leads to, for example, a decrease in transmittance and an increase in resistance value due to excessive structural relaxation. Further, the addition of less than 0.01% by volume is not desirable because it is difficult to control the addition amount.

These nitrogen, carbon dioxide, carbon monoxide,
The addition amount of the gas consisting of water, ammonia, laughing gas, nitrogen dioxide and methane can be controlled by monitoring the partial pressure.

The gas partial pressure at the time of sputtering can be measured by using a differential exhaust type in-process monitor or a broadband quadrupole mass spectrometer. The broadband quadrupole mass spectrometer is simple to operate and does not take up much space.

The thickness of the formed transparent conductive film is desirably about 130 nm in order to provide an electrode substrate having a reduced resistance value and to improve optical characteristics. In particular, if a transparent conductive film having a low surface resistance is required, the thickness may be about 260 nm. However, if the thickness exceeds 300 nm, the flexibility of the polymer substrate may not be able to withstand the compressive stress of the crystallized transparent conductive film, and the warpage of the substrate may become extremely large. Alternatively, cracks may occur in the transparent conductive film due to compressive stress. For this reason,
It is desirable to control the film thickness to 300 nm or less.

In the transparent conductive film according to the present invention, a favorable pattern can be obtained by having a specific resistance of 4.0 to 10.0 × 10 ⁻⁴ Ω · cm before etching. Then, the transparent conductive film is converted into crystalline by a heat treatment step in the liquid crystal cell forming process after the etching so as to exhibit a specific resistance of 1.0 to 3.5 × 10 ⁻⁴ Ω · cm, so that the transparent conductive film can be applied to the electrode substrate. Wide voltage range. More desirably, 1.0 to 3.0 × 10 ⁻⁴ Ω ·
cm specific resistance.

As described above, according to the present invention, by precisely controlling the crystallization process of the transparent conductive film, it is possible to avoid the trade-off relationship between the etching characteristics and the reduction of the resistance value, and to obtain a low specific resistance advantageous for the process environment. It has a feature that an electrode substrate having a transparent conductive film can be provided.

[0080]

According to the present invention, by providing an amorphous transparent conductive film on a polymer substrate, patterning is easy, and the film can be converted into a low-resistivity transparent conductive film by heat treatment after the etching step. It has become possible to provide an electrode substrate with low resistance. Since this electrode substrate has a small specific resistance, it can be preferably used not only for monochrome display but also as a component for multi-color display.

[0081]

The present invention will be described in more detail with reference to the following examples. Since there is a strong correlation between the etching characteristics and the X-ray reflection intensity, which is an index of the crystallinity, the present invention uses X
The etching characteristics are inferred by monitoring the line reflection intensity. In the present invention, the X-ray reflection intensity is 10
Below 00 cpm, it is not crystallized and the reflection intensity is 10
If it exceeds 00 cpm, it means that it is crystallized.

[Measurement method] (Measurement of X-ray intensity) The X-ray reflection intensity in the present invention was measured by Riga.
The measurement was carried out using a Kutta Rotaflex RU-300 with a Bragg-Brentano optical configuration. The light source is CuKα ray (wavelength: 1.541 °) of 50 kV,
Using a power of 200 mA, a divergence slit 1 °, a light receiving slit 1 ° and a scattering slit 0.15 ° were employed as an optical system. A graphite monochromator was also used. The diffraction line from the (222) plane of the ITO film is C
When uKα ray is used, it appears at a position of about 30.5 ° (2θ). The X-ray diffraction intensity from the (222) plane of the ITO film was measured in the range of 29 to 32 ° (2θ) in 0.05 ° steps, and it was measured over 1 second per step.

The X-ray reflection intensity from the (222) plane obtained from the obtained X-ray diffraction pattern was used as a representative value of the etching characteristics. When the X-ray reflection intensity is 1000 cps (count / second) or less, favorable etching can be performed by the etchant used in the present invention. Further, it is desirable that the reflection intensity from the (222) plane before etching is small.

(Measurement of Surface Resistance and Specific Resistance) The surface resistance of the ITO film was measured by Mitsubishi Chemical's Loest, a four-terminal resistance meter.
a Measured using MPMCP-T350. The specific resistance was calculated from the surface resistance and the film thickness.

(Measurement of Film Thickness of ITO Film) The film thickness of the ITO film was measured by using the film thickness of the film formed on glass under the same conditions as the film forming conditions of the embodiment and the comparative example. Was measured using Dektak, and the sputter rate was determined and calculated from this.

(Measurement of partial pressure of gas when forming ITO film)
The gas partial pressure at the time of film formation is MP manufactured by MC Electronics.
Monitored using an A mass spectrometer.

Table 1 summarizes the results of the examples and comparative examples.

Example 1 A 100 micron polycarbonate substrate coated on both sides so as to have acid resistance, alkali resistance, and organic solvent resistance was treated with 130 n
An ITO film containing 5% by weight of SnO ₂ was formed by a DC magnetron sputtering method. Water was added simultaneously with Ar and oxygen at a concentration of 0.06% by volume with respect to Ar. The specific resistance of the transparent conductive film immediately after the film formation was 5.2 × 10 ⁻⁴ Ω · cm. The reflection intensity from the (222) plane by X-ray diffraction was not observed.

The electrode substrate was placed in a thermostat at 110 ° C. for 60 hours.
Heat treatment (pre-baking) for (222) plane
Had a reflection intensity of 850 cps. Specific resistance is 5.0X
10 ^-FourΩ · cm. 12% by weight aqueous hydrogen chloride solution
(12% by weight hydrochloric acid) and 12% by weight aqueous ferric chloride solution
And an aqueous etchant (12% by weight
At 25 ° C liquid temperature, and etch the electrode substrate.
The etching results in good etching characteristics.
Was.

After that, a heat treatment was performed for 4 hours in a thermostat at 130 ° C., and the specific resistance of the transparent conductive film was 2.6 ×.
It became 10 ^-4 Ω · cm. The X-ray reflection intensity is 840.
It was 0 cps.

Example 2 100-micron 1,1-bis (4-hydroxyphenyl) -3,3,5-coated on both sides so as to have acid resistance, alkali resistance and organic solvent resistance. 5% by weight of 130 nm on a copolymer of trimethylcyclohexane and bisphenol
An ITO film containing SnO ₂ was formed and formed. Water was added simultaneously with Ar and oxygen at a concentration of 0.06% by volume with respect to Ar. The specific resistance is 5.3 × 10 ⁻⁴ Ω · cm and (22
2) No reflection intensity from the surface was observed.

This electrode substrate was subjected to a heat treatment (pre-bake) for 60 minutes in a thermostat at 90 ° C.
2) The reflection intensity from the surface was 100 cps. The specific resistance was 5.3 × 10 ⁻⁴ Ω · cm. An aqueous solution etchant (12% by weight) obtained by mixing a 12% by weight aqueous hydrogen chloride solution (12% by weight hydrochloric acid) and 12% by weight ferric chloride.
When the electrode substrate was etched at a liquid temperature of 25 ° C. using an etchant), good etching characteristics were obtained.

After that, a heat treatment was performed for 2 hours in a thermostat at 150 ° C., and the specific resistance of the transparent conductive film was 2.7 ×.
It became 10 ^-4 Ω · cm. The X-ray reflection intensity is 750
It was 0 cps.

Example 3 Coating of 100 micron 9,9-bis (4-hydroxyphenyl) fluorene with bisphenol A, which was coated on both sides to have acid resistance, alkali resistance, and organic solvent resistance. An ITO film containing 10% by weight of SnO _{2 and} having a thickness of 130 nm was formed on the polymer polymer. Water was added simultaneously with Ar and oxygen at a concentration of 0.08% by volume with respect to Ar. The specific resistance is 6.4X1
0 ⁻⁴ Ω · cm, and no reflection intensity from the (222) plane was observed.

The electrode substrate was subjected to a heat treatment (pre-bake) for 60 minutes in a thermostat at 90 ° C.
2) No reflection intensity from the surface was observed. The specific resistance was 6.2 × 10 ⁻⁴ Ω · cm. Using an aqueous solution etchant (12% by weight etchant) obtained by mixing a 12% by weight aqueous hydrogen chloride solution (12% by weight hydrochloric acid) and 12% by weight ferric chloride, at a liquid temperature of 25 ° C., the electrode substrate When etching was performed, good etching characteristics were obtained.

After that, a heat treatment was performed for 2 hours in a thermostat at 150 ° C., and the specific resistance of the transparent conductive film was 2.3X.
It became 10 ^-4 Ω · cm. The X-ray reflection intensity is 570
It was 0 cps.

Example 4 A 100 μm polycarbonate substrate coated on both sides so as to have acid resistance, alkali resistance and organic solvent resistance was treated with 130 n
An ITO film containing 10% by weight of SnO ₂ was formed by a DC magnetron sputtering method. Only Ar and oxygen were used as the process gas. The specific resistance of the transparent conductive film immediately after the film formation was 7.2 × 10 ⁻⁴ Ω · cm. The reflection intensity from the (222) plane by X-ray diffraction was not observed.

The electrode substrate was placed in a thermostat at 110 ° C. for 60 hours.
Heat treatment (pre-baking) for (222) plane
Had a reflection intensity of 500 cps. The specific resistance is 6.8X
10 ^-FourΩ · cm. 8% by weight aqueous hydrogen chloride solution
(8% by weight hydrochloric acid) and 8% by weight ferric chloride
Aqueous solution etchant (8% by weight etchant)
Performs electrode substrate etching at a liquid temperature of 25 ° C.
As a result, good etching characteristics were obtained.

After that, a heat treatment was performed for 4 hours in a thermostat at 130 ° C., and the specific resistance of the transparent conductive film was 2.4 ×.
It became 10 ^-4 Ω · cm. The X-ray reflection intensity was 650.
It was 0 cps.

[Comparative Example 1] A 100 micron polycarbonate substrate coated on both sides so as to have acid resistance, alkali resistance, and organic solvent resistance was treated with 130 n
An ITO film containing 5% by weight of SnO ₂ was formed by a DC magnetron sputtering method. Water was added simultaneously with Ar and oxygen at a concentration of 0.005% by volume with respect to Ar. The specific resistance of the transparent conductive film immediately after film formation is 4.0 × 10 ⁻⁴ Ω · cm.
Met. The reflection intensity from the (222) plane by the X-ray diffraction method was 350 cps.

The electrode substrate was placed in a thermostat at 110 ° C. for 60 hours.
Heat treatment (pre-bake) for (22
2) The reflection intensity from the surface was 4000 cps. The specific resistance was 3.8 × 10 ⁻⁴ Ω · cm. Using an aqueous solution etchant (20% by weight etchant) obtained by mixing a 20% by weight aqueous solution of hydrogen chloride (20% by weight of hydrochloric acid) and 20% by weight of ferric chloride, at a liquid temperature of 25 ° C., the electrode substrate However, etching was not performed. When the etchant was heated to 50 ° C., etching could be performed. However, the electrode substrate was sometimes slightly damaged.

Thereafter, when heat treatment was performed at 130 ° C. for 4 hours, the specific resistance did not change. In addition, it was determined that the substrate might be damaged and was not suitable for practical use.

[0103]

[Table 1]

Claims (8)

[Claims] 1. A method for manufacturing an electrode substrate, comprising: etching a transparent conductive laminate having a transparent conductive film formed on a polymer substrate and patterning the transparent conductive film. Without crystallization
A method for manufacturing a patterned electrode substrate, comprising crystallizing a transparent conductive film after an etching process. 2. The method according to claim 1, further comprising a step of performing a heat treatment at 130 to 200 ° C. after the step of patterning the transparent conductive film by etching. 3. 3.5 to 20% by weight of the etchant component
3. The electrode substrate according to claim 1, wherein an aqueous solution containing hydrogen chloride as an etchant component is used as an etchant, and the etching process is performed while maintaining the etchant at a temperature of 30 ° C. or less. Manufacturing method. 4. 0.75 to 1 part by weight of hydrogen chloride
The ferric chloride is contained as an etchant component in a proportion of 1.25 parts by weight.
The method for producing an electrode substrate according to any one of the above. 5. A heat treatment at 130 to 200 ° C. for 120 to 3 hours.
The method for producing an electrode substrate according to claim 2, wherein the method is performed for 00 minutes. 6. The transparent conductive film according to claim 1, wherein the transparent conductive film is mainly composed of indium (In), tin (Sn) and oxygen atoms (O). Of manufacturing an electrode substrate. 7. The method for manufacturing an electrode substrate according to claim 1, wherein a specific resistance of the transparent conductive film before the etching treatment is 4.0 to 10.0 × 10 ⁻⁴ Ω · cm. Method. 8. The electrode according to claim 1, wherein the resistivity of the transparent conductive film after the heat treatment after the etching treatment is 1.0 to 3.5 × 10 ⁻⁴ Ω · cm. Substrate manufacturing method.