JPH10241464A - Substrate with transparent conductive film and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce specific resistance, enhance durability, and enhance fine electrode working performance by including ZnO and In2 O3 in a transparent oxide layer so that the content of In2 O3 is 30 molar % or more based on the total amount of ZnO and In2 O3 , and including Ag in a metal layer. SOLUTION: Transparent oxide layers 2, 4, 6 contain ZnO and In2 O3 so that the content of In2 O3 is 30 molar % or more based on the total amount of ZnO and In2 O3 . The transparent oxide layers other than the transparent oxide layer farthest from a substrate 1 (2n+1)th layer from the substrate, (n) is an integer of 1 and more either} contain In2 O3 of 30 molar % or more but less than 90 molar % based on the total amount of ZnO and In2 O3 . As a result, moisture resistance and fine electrode pattern working capability with an acidic aqueous solution can be increased. By constituting a metal layer with films 3, 5 having Ag as the main component, chemical durability, especially durability to alkaline solution can furthermore be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate with a transparent conductive film used for a liquid crystal display (hereinafter, referred to as LCD) and the like and a method for producing the same.

[0002]

2. Description of the Related Art At present, ITO (In) is used as an electrode for LCD.
And mixed oxide (Sn) films are widely used. In particular, with STN-type color LCDs, as the definition and size of the screen increase, the line width of the liquid crystal drive transparent electrode is required to be narrower and longer. Therefore, an extremely low-resistance transparent conductive film having a sheet resistance of about 3Ω / □ is required. In order to achieve this sheet resistance, it is necessary to increase the thickness of the transparent conductive film (300 nm or more) or reduce the specific resistance (100 μΩ · cm or less).

[0003] However, increasing the film thickness involves 1) increasing the cost of forming a transparent conductive film, 2) increasing the difficulty of electrode patterning, and 3) increasing the level difference due to the presence or absence of a transparent conductive electrode, resulting in an increase in the level of the liquid crystal. There is a limit due to problems such as difficulty in controlling the orientation.

On the other hand, a method of reducing the specific resistance of the ITO film itself has been studied, but a method of stably producing a low specific resistance ITO film of 100 μΩ · cm or less has not yet been established. On the other hand, as a method for easily obtaining a low specific resistance transparent conductive film of 100 μΩ · cm or less, a configuration of ITO / Ag / ITO in which an Ag layer is sandwiched between ITO layers is known. However, although this configuration also has a low specific resistance, its durability is insufficient enough to cause white defects which are considered to be film peeling when left indoors. Further, when the electrode is processed by etching using an acidic aqueous solution, the side etching progresses and peeling is observed at the pattern edge portion, and the workability is insufficient.

[0005] For this reason, although a substrate having an ITO / Ag / ITO structure has an advantage that a low specific resistance can be easily obtained, it has not been practically used as a transparent conductive substrate for LCD.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a substrate with a transparent conductive film which is used in LCDs and the like, has a low specific resistance, is excellent in durability, and is excellent in fine electrode processing performance, and a method for producing the same. And

[0007]

According to the present invention, a transparent oxide layer and a metal layer are formed on a substrate in this order from the substrate side (2n +
1) In a substrate with a transparent conductive film formed by stacking layers (n is an integer of 1 or more), the transparent oxide layer is made of ZnO and In ₂ O.
₃ and the content ratio of In ₂ O ₃ is ZnO and In ₂ O _3.
The present invention provides a substrate with a transparent conductive film and a method for producing the same, wherein the metal layer is at least 30 mol% with respect to the total amount of O ₃ and the metal layer is a metal layer containing Ag.

FIG. 1A is a cross-sectional view of the substrate with a transparent conductive film of the present invention when n = 1, and FIG. 1B is when n = 2. 1 is a substrate, and 2, 4 and 6 are transparent oxide layers. Transparent oxide layer 2, 4, 6 comprises ZnO and In ₂ O _3, an In content of ₂ O ₃ is an oxide layer of 30 mol% or more based on the total amount of ZnO and In ₂ O ₃ It is.

Further, the transparent oxide layers other than the transparent oxide layer farthest from the substrate (that is, the (2n + 1) th transparent oxide layer) are made of ZnO and In ₂ O from the viewpoint of alkali resistance.
₃ and the content ratio of In ₂ O ₃ is ZnO and In ₂ O _3.
It is preferable that the content is 30 mol% or more and less than 90 mol% based on the total amount of O ₃ .

By the way, when the atomic ratio of In / (In + Zn) is A (%), In ₂ O ₃ / (In ₂ O ₃ + ZnO)
A = (2B / (2B +
(100-B)) × 100. Therefore, Z
In ₂ O ₃ 30 mol% relative to the total amount of nO and In ₂ O ₃ becomes 46.2 atomic% in the atomic ratio of In / (In + Zn).

Since ZnO is easily crystallized, Ag crystallization is promoted even under a low-temperature film formation condition of 150 ° C. or less as compared with the case where a conventional ITO film is used.
Not only prevents the agglomeration phenomenon, but also improves the adhesive force at the interface between ZnO and Ag, and as a result, significantly improves the moisture resistance and the processability of the fine electrode pattern with an acidic aqueous solution (hereinafter referred to as patternability). In this case, it is preferable that the film containing Ag as a main component and the film containing ZnO as a main component be in contact with each other, or the film containing Ag as a main component and a layer rich in a ZnO component are preferably in contact with each other. .

Reference numerals 3 and 5 denote metal layers containing Ag as a main component. By containing In ₂ O ₃ in the oxide layer, the aforementioned Z
In addition to the excellent characteristics of nO, the chemical durability, particularly the durability against an alkaline solution, is improved.

As the substrate 1 in the present invention, a glass plate, a resin film or the like is used. Further, a substrate as shown in FIG. 2 is also used. FIG. 2 shows a substrate for a color LCD corresponding to the base 1 of FIG. 39 is a glass substrate, 7 is a color filter layer serving as a color pixel, 8 is a transparent resin protective layer, and 9 is an inorganic intermediate film layer. Transparent resin layer 8
Protects and smoothes the color filter layer. The inorganic intermediate film layer 9 is for improving the adhesion between the transparent resin layer 8 and the transparent conductive film, and is made of silica, SiN _x or the like.

The transparent oxide layer is composed of 1) In ₂ O ₃ and ZnO
Or 2) a layer composed of a multilayer film composed of a film 10 composed mainly of In ₂ O ₃ and a film 11 composed mainly of ZnO, as shown in FIG. Preferably, there is.

In the transparent oxide layer, In ₂ O ₃ contains S
n or the like can be added. A trivalent dopant such as Ga or Al can be added to ZnO in the transparent oxide layer.
When a trivalent dopant is added to ZnO, which is an insulator, conductivity is exhibited, but the addition of Ga exhibits the best conductivity and visible light transmittance.

The content ratio of Ga is preferably 1 to 15 atomic% with respect to the total amount of Zn and Ga. If it is less than 1% by atom, the film forming rate is low, and if it exceeds 15% by atom, the visible light transmittance is low. The thickness of each transparent oxide layer is
From the viewpoint of color tone and visible light transmittance, 10 to 200 nm
Is preferred.

The transparent oxide layer may be a layer composed of a multilayer film. That is, for example, the transparent oxide layer 2 may have a film containing In ₂ O ₃ as a main component, and may be composed of a total of two or more layers. The total thickness of the transparent oxide layer 2 is preferably from 10 to 200 nm. Also in this case, in the transparent oxide layer 2, In
Content of ₂ O ₃ is to be formed so as to be 30 mol% or more based on the total amount of ZnO and an In ₂ O _3.
The thickness ratio of the film mainly composed of In ₂ O ₃ to the total thickness of the transparent oxide layer 2 is set so that the content ratio of In ₂ O ₃ satisfies the above.

More specifically, the transparent oxide layer 2 is made of In
A case is considered in which a film mainly composed of ₂ O ₃ and a film mainly composed of ZnO are composed of a total of five layers in which five layers are alternately laminated in this order. In the entire five layers, the content ratio of In ₂ O ₃ is Z
The content is set to 30 mol% or more based on the total amount of nO and In ₂ O ₃ . When the transparent oxide layer 2 is composed of the above-mentioned multilayer film, it is realized by controlling the thickness ratio of the film mainly composed of In ₂ O ₃ to the total film thickness.

With this configuration, not only good moisture resistance and patterning characteristics can be obtained, but also alkali resistance is improved. It is preferably at least 50 mol%. In this specification, “film thickness” means not an optical film thickness but a geometric film thickness.

As the transparent oxide layer farthest from the substrate,
a) using a layer composed of a multilayer film formed in the order of a film mainly composed of ZnO and a film mainly composed of In ₂ O ₃ from the substrate side, or b) a mixture of In ₂ O ₃ and ZnO It is preferable to use an oxide layer having a gradient composition in which the content of In ₂ O ₃ increases in the thickness direction as the distance from the substrate increases. By adopting the configuration of a) or b), corrosion and durability against an alkaline solution are excellent.

In particular, it is preferable that the transparent oxide layer furthest from the substrate has an In ₂ O ₃ rich layer composed of an oxide containing In ₂ O ₃ as a main component. As the In ₂ O ₃ rich layer, 1) ZnO and In ₂ O ₃ are contained, and ZnO and I
a layer containing 90 mol% or more of In ₂ O ₃ with respect to the total amount of n ₂ O ₃ , 2) a layer consisting of only Sn-added In ₂ O ₃ (ITO), or 3) a layer consisting of only In ₂ O ₃ It is preferably a layer.

The In ₂ O ₃ rich layer is preferably formed on the air side opposite to the substrate. The thickness of the part is
From the viewpoint of patterning characteristics and moisture resistance, 5 to 30 n
m, preferably 5 to 20 nm. For example, as shown in FIG. 4, an ITO film 12 is formed as an In ₂ O ₃ rich layer on the air side of the transparent oxide layer 6 farthest from the base. The addition ratio of Sn is S
15 atomic% or less in terms of n / (In + Sn) ratio (that is, S
nO ₂ / (In ₂ O ₃ + SnO ₂ ) ratio is preferably 26 mol% or less.

The above 1) contains ZnO and In ₂ O ₃ ,
In ₂ O ₃ is 90 with respect to the total amount of ZnO and In ₂ O _3.
In the case of using a layer of not less than mol%, Sn may be added to In ₂ O ₃ . The addition ratio of Sn is preferably within the above range. The alkali resistance is improved by enrichment of the In ₂ O ₃ component. The addition of ZnO improves the patterning property and the moisture resistance. Also, Sn
The conductivity is improved by adding O ₂ . Therefore, from the viewpoint of alkali resistance, as In ₂ O ₃ rich layer, it is preferable to use a layer made of only In ₂ O _3.

A preferred specific configuration in the present invention will be described below. That is, five layers of a transparent oxide layer and a metal layer are laminated in this order, the fifth transparent oxide layer counted from the substrate side is composed of a lower layer and an upper layer, and the lower layer is Zn.
O and In ₂ O _3, and the content ratio of In ₂ O ₃ is Z
30 mol% or more based on the total amount of nO and In ₂ O ₃ and 90
Preferably, the oxide layer is less than mol%, and the upper layer is an In ₂ O ₃ rich layer. As the In ₂ O ₃ rich layer, any one of the above-mentioned layers 1) to 3) is appropriately selected and used according to expected characteristics.

The first and third transparent oxide layers other than the fifth transparent oxide layer have the following properties from the viewpoint of alkali resistance.
And a ZnO and In ₂ O _3, the content of In ₂ O ₃ is preferably less than 30 mol% to 90 mol% based on the total amount of ZnO and In ₂ O _3. The thickness of each transparent oxide layer is 10 to 50 nm for the first layer and 60 to 60 nm for the third layer, counted from the substrate side, since a high transmittance is obtained.
It is preferable that the thickness of the fifth layer is 120 nm, and the thickness of the fifth layer is 20 to 60 nm.

In the present invention, one or more of the metal layers is 1)
A layer composed of an alloy film of Ag and another metal, 2) a multi-layered layer composed of a layer mainly composed of Ag and another metal layer, or 3) a layer composed of Ag and another metal, A in the thickness direction
Preferably, the layer has a gradient composition in which the g concentration changes. In the case of the above 2), for example, it is also preferable that another metal layer is configured to be interposed at the interface with the transparent oxide layer. When there are a plurality of interfaces, it is configured to intervene at least one interface.

As described above, the metal layer is composed of 1) an alloy layer,
2) a multilayer composition layer or 3) a gradient composition film,
The moisture resistance due to the aggregation phenomenon of Ag can be improved without impairing low specific resistance and high visible light transmittance. 1)
3), the thickness of the metal layer is 3 to 20.
It is preferably nm. If it is less than 3 nm, the sheet resistance increases, and if it exceeds 20 nm, the visible light transmittance is reduced.

As for other metals, Pd, Au, Cu, Zn, Sn, Ti, Z
One or more selected from the group consisting of r, V, Ni, Cr, Pt, Rh, Ir, W, Mo, and Al are preferred.
In particular, the other metal is preferably Au and / or Pd. By adding Au or Pd, the aggregation phenomenon of Ag is prevented, and a highly durable Ag film is obtained.

The structure of the above metal layers 1) to 3) will be specifically described using Pd as another metal. As the configuration of the above 1), an Ag layer containing Pd (PdAg
Alloy layer). Pd is uniformly present in Ag in the alloy film. In this case, the content ratio of Pd in the metal layer is 0.1 to
It is preferably 5.0 atomic%. If it is less than 0.1 atomic%, the durability is insufficient, and if it exceeds 5.0 atomic%, the visible light transmittance is reduced and the specific resistance is increased.

5A, a Pd layer (intervening layer) 15 is formed at the interface between the transparent oxide layers 2 and 4 and the metal layer 16 mainly composed of Ag, as shown in FIG. , 17 are interposed locally. In this case, the thickness range of the intervening layers 15 and 17 is preferably 0.1 to 1 nm. By interposing with this thickness, the same effect as the effect of adding Pd in 1) can be obtained. If the thickness of the metal layer other than Ag is less than 0.1 nm, the durability is insufficient, and if it exceeds 1 nm, the visible light transmittance is reduced.

FIG. 6A shows the configuration of the above 2).
As shown in FIG. 2, the layer 22 mainly composed of Ag and the Pd layer 21
And a multilayer structure. In this case, it is preferable that the thickness of the Pd layer 21 be 0.1 to 3 nm and the thickness of the layer 22 containing Ag as a main component be 1 to 20 nm.

As the structure of the above 3), as shown in FIG. 5B or FIG. 6B, a layer having a gradient composition in which the Ag concentration changes in the thickness direction of the layer is used. In this case, Pd
The structure in which the Pd-rich layers 18 and 20 in which the metal concentration becomes high is interposed, and as shown in FIG.
A multi-layer configuration of d-rich layers is used. As shown in FIG. 5A, the Pd-rich layers 18, 20, 23, and 24 are layers in which Pd is 50 atomic% or more with respect to the sum of Ag and Pd. The thickness of the Pd-rich layer is 0.1
If it is less than 3 nm, the durability is insufficient, and if it exceeds 3 nm, the visible light transmittance tends to decrease.
A thickness of m is appropriate.

By selecting the thickness of each layer constituting the transparent conductive film within the above range, it is possible to adjust the transmittance, the color tone, and the sheet resistance by the optical interference effect.

The transparent conductive film according to the present invention has low sheet resistance, high visible light transmittance and high durability. However, in order to further improve the characteristics, the transparent conductive film may be subjected to a heat treatment at 100 to 300 ° C. after film formation. Good. By this heat treatment, crystallization and stabilization of the oxide layer are promoted, lower resistance and higher visible light transmittance are obtained, and heat resistance is also improved. In particular, it is very effective to perform the above-described heat treatment on the transparent conductive film formed by sputtering. The heat treatment time is preferably 30 to 60 minutes. Further, the heating atmosphere is preferably an oxidizing atmosphere such as the air.

The transparent conductive film according to the present invention can be used for an electroluminescent display (E.
It is most suitable as a substrate with a transparent electrode film of an electronic display requiring a low resistance, such as an LD, a plasma display (PDP), or an electrochromic device (ECD). In particular, in a simple matrix type LCD, by using the substrate with a transparent conductive film of the present invention, an excellent effect of improving display quality such as enlargement of a display area and reduction of crosstalk is exhibited.

After the transparent conductive film is formed on the substrate, the transparent electrode can be formed by etching and patterning using a 0.01 to 5N acidic aqueous solution. The transparent electrode is suitable as a transparent electrode of a transparent conductive substrate for various displays such as an LCD.

FIG. 1 shows a first patterning method.
After forming a desired resist pattern by a photolithography method on a transparent conductive laminated film as shown in
Etching and patterning may be performed using an acidic aqueous solution of up to 5N. Etching hardly proceeds in an acidic aqueous solution of less than 0.01 N, and side etching proceeds in an acidic aqueous solution of more than 5 N. Examples of the acidic aqueous solution include an aqueous solution mainly containing hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid, and ferric chloride. In particular, an acidic aqueous solution containing ferric chloride (FeCl ₃ ) as a main component is preferable because of its high etching rate and small side etching.

In addition, since the metal layer containing Ag as a main component can be efficiently etched, an oxidizing agent having a noble redox potential (having an oxidizing effect on Ag) than Ag is added to the above acidic aqueous solution. It is preferred to add. By adding the oxidizing agent, the dissolution rate of Ag can be increased, and better patterning performance can be obtained.

Examples of the oxidizing agent include nitrous acid, hydrogen peroxide, potassium permanganate, potassium iodate, ceric ammonium nitrate and the like. In this case, 0.0
It is preferable to add 0.005 to 0.5N oxidizing agent to the 5 to 2N acidic aqueous solution. If the concentration is out of this range, the etching of the metal layer becomes difficult to proceed, resulting in an etching residue or side etching.

FIG. 7 shows a second patterning method.
As shown in FIG. 3, a desired pattern is formed on a substrate using a resist 26 soluble in an alkaline solution or an organic solvent, and then the transparent conductive film is formed. A method of stripping an unnecessary portion of the transparent conductive film together with the resist 26 may be used. Examples of the resist 26 soluble in an alkali solution or an organic solvent include those obtained by dissolving a novolak resin containing a photosensitive material in an organic solvent such as ethylene glycol monoethyl ether monoacetate.

As the alkaline solution as the stripping solution, N
An alkaline aqueous solution containing 0.5 to 3% by weight of aOH based on the solution, an alkaline aqueous solution containing 2 to 3% by weight of tetramethylammonium hydroxide based on the solution, o-dichlorobenzene, phenol and alkylbenzenesulfonic acid Organic alkali solution. Examples of the organic solvent as the stripping solution include organic solvents such as isopropyl alcohol, dimethyl sulfoxide, ethylene glycol, and trichloroethylene. Both the resist and the stripper are not particularly limited as long as they do not damage the transparent conductive film or the substrate. As a method for forming the transparent conductive film after the formation of the resist pattern, it is preferable to form the film at a substrate temperature of 150 ° C. or lower in order to avoid thermal damage to the resist.

The features of the first patterning method described above are that an arbitrary electrode pattern after film formation can be formed.
There is no deterioration in film characteristics due to outgassing from the resist during film formation. On the other hand, the features of the second patterning method are that the composition of the complicated etching solution, the optimization of the etching conditions are not required, the etching residue such as a reaction product with an acid is small, the high patterning accuracy and the good pattern shape. Is obtained.

The transparent conductive film of the present invention can be applied to a thin film transistor type LCD as shown in FIG. That is, the source electrode 32, the drain electrode 31, and the pixel electrode 30 of the conventional thin film transistor type liquid crystal display shown in FIG. 8A can be formed of the transparent conductive film. Further, after forming a gate electrode 27, a gate insulating film 28, and a semiconductor layer 29 on the base, the transparent conductive film is formed,
Next, by etching the transparent conductive film, a drain electrode 33 integrated with the source electrode 32 and the pixel electrode 30 can be formed as shown in FIG.
By using the transparent conductive film as the source electrode 32, the drain electrode 31, and the pixel electrode 30, batch formation and patterning of the source, drain, and pixel electrodes can be performed, thereby improving productivity and reducing defects. Demonstrates excellent effects.

[0044]

【Example】

[Examples 1 to 15] Hereinafter, Examples 2 to 5, 7 to 11, and 14 to 15 correspond to Examples, and Examples 1, 6, and 12 to 13 correspond to Comparative Examples. As shown in FIG. 2, a glass substrate 39, a color filter layer 7, an acrylic resin layer protective layer 8 for protecting and smoothing the color filter, and a silica film 9
Was formed on the substrate 1 on which was previously formed without heating the substrate by a DC sputtering method without heating the substrate.

[0045] In ₂ in forming the film composed mainly of In ₂ O ₃ is containing 10 atomic% "Sn in In ₂ O ₃ (hereinafter examples and Tables 1-2 containing Sn 10 atomic% O
₃ ) was abbreviated as "ITO") and a film target was formed in an atmosphere of 3 mTorr of Ar gas containing 3% oxygen using a sintered target or an In ₂ O ₃ sintered target.

When a film containing ZnO as a main component is formed, a ZnO sintered body target containing 5 atomic% of Ga (refer to “Z containing 5 atomic% of Ga” in the following examples and Tables 1 and 2).
nO ”is abbreviated as“ GZO ”), and an Ar gas of 3 m
The film was formed in an atmosphere of Torr.

In forming a mixed oxide film, In ₂ O
_A film was formed in an atmosphere of 3 mTorr of Ar gas containing 3% oxygen using a target of mixed oxide having a molar ratio of ₃ to ZnO of 2: 8, 7: 3, 9: 1.

The metal layer is made of an Ag alloy containing Pd, Ag and 1 atomic% of Pd (“1” in the following examples and Tables 1 and 2).
"Ag alloy containing at.% Of Pd" is abbreviated as "PdAg"), or Ag alloy containing 1 at.% Of Au (in the following examples and Tables 1 and 2, "Ag containing 1 at.% Of Au").
Alloy "is abbreviated as" AuAg ").
The film was formed in an atmosphere of Ar gas at 3 mTorr. The thickness of each film was adjusted by the sputtering power and the film formation time.

In Examples 5, 6, 7, and 9, the transparent oxide layer was composed of multiple layers, and the multilayers A1 to A5 were formed of In ₂ O ₃ / (In
₂ O ₃ + ZnO) was set to 70 mol%, and the thickness ratio of each of the multilayers B1 and B2 was set to 20 mol%. For the films other than those of Example 11, a heat treatment was performed at 250 ° C. for 30 minutes in the air after the film formation.

For the samples of Examples 1 to 15, 1) sheet resistance ("resistance" in Table 3), 2) visible light transmittance ("transmittance" in Table 3), 3) patterning property, 4) moisture resistance Table 3 shows the results of evaluation of the properties 5) and alkali resistance.
Table 5 shows conditions for evaluating 3) patterning properties and 4) moisture resistance, and Table 4 shows conditions for evaluating 5) alkali resistance.

In the patterning, a resist is applied after the formation of the transparent conductive film, and a striped resist pattern having a line width of 130 μm and a space width of 20 μm is formed by photolithography. The etching was performed using an etching aqueous solution consisting of diiron and 3.8 mol / liter of hydrochloric acid.

When the transparent conductive films shown in Examples 1 to 12 and 14 to 15 were used, they had a sharp pattern edge shape, hardly any etching residue, and had a good side etching amount of about 2 to 4 μm. Patterning properties were obtained. With respect to moisture resistance, no defect of 0.5 mm or more was observed, and good performance was obtained. With respect to the alkali resistance, extremely good results were obtained with the film configurations of Examples 7 to 11 and 14 to 15.

The film containing Ag as the main component shown in Example 13 was replaced by IT
In a film having a configuration sandwiched between O films, the peeling at the interface between the metal film and the ITO film is severe, a desired electrode pattern cannot be obtained, and many defects of 1 mm or more are generated in the moisture resistance test. No results were obtained. Example 10 and Example 11 have the same film composition, but in Example 10, heat treatment after film formation reduced the specific resistance and improved the transmittance.

Similar effects were obtained when the transparent oxide layers of the transparent conductive films shown in Examples 1 to 11 and 14 to 15 were replaced with transparent oxide layers having a gradient composition.

Example 16 (Example) A substrate as shown in FIG. 2 was prepared as a color filter substrate. As the color filter layer 7 on the glass substrate 39, three colors of RGB were formed by a pigment dispersion method. The color filter layer 7 can be formed by a known method such as a printing method, an electrodeposition method, and an ink jet method, in addition to the present method.

The insulating layer 8 on the color filter layer 7 also serves as a flattening layer for smoothing the unevenness of the color filter layer.
Specifically, resins such as acrylic resin, epoxy resin, silicone resin, polyimide, and polyamide are used.
In this example, an acrylic resin was used.

Further, SiO ₂ , SiN, Ti is formed on the insulating layer 8 for the purpose of improving the bonding property with the transparent conductive film.
An inorganic film 9 such as O ₂ may be formed, but was not formed in this example. A transparent conductive film was formed on the insulating layer 8 in the same manner as in Example 2. Next, a resist having a desired pattern was formed by a photolithography method, and the resist was etched with an etching solution containing ferric chloride and hydrochloric acid to form a desired linear transparent electrode pattern. Thereafter, an alignment film of polyimide was applied on the transparent electrode, dried, and subjected to an alignment treatment by rubbing.

On the other hand, as a substrate on the opposite side, a transparent electrode was formed on a glass substrate in the same manner as described above, and an orientation treatment was performed. Thereafter, a liquid crystal was injected and sealed between the two electrodes obtained as described above to produce a simple matrix STN liquid crystal display element. As a result, the brightness gradient and the shadowing were significantly reduced and the display performance of the liquid crystal display element was improved as compared with the conventional device using the ITO electrode (sheet resistance 5Ω / □).

Example 17 (Example) In the production of the liquid crystal display device of Example 16, the transparent conductive film of Example 2 was replaced with the transparent conductive film of Examples 3 to 5, and 7.
A liquid crystal display device was produced in the same manner as in Example 16, except that the transparent conductive films of Examples 11 to 14 and 15 were respectively changed.
In each case, the same good results as in Example 16 were obtained.

Example 18 (Example) In the production of the liquid crystal display element of Example 16, a transparent electrode made of the transparent conductive film of Example 2 was formed only on the color filter substrate side, and a conventional ITO was used as the opposing electrode. A liquid crystal display device was produced in the same manner as in Example 16 except that the electrodes were used, and good results were obtained as in Example 16.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

[Table 5]

[0066]

According to the present invention, when the total thickness of the transparent conductive laminated film is 300 nm or less, a low sheet resistance of about 3 Ω / □ can be easily obtained, and the durability such as alkali resistance and moisture resistance can be easily obtained. A substrate with a transparent conductive film having excellent resistance can be provided.

Since a transparent conductive laminated film can be formed not only on glass but also on plastic having a low film forming temperature (100 ° C. or lower) or on a substrate with a color filter for color LCD (250 ° C. or lower), the Including
It is optimal as a transparent electrode film for an electronic display requiring a low resistance such as ELD, PDP, or ECD, and can be provided at a lower cost than in the past. In particular, in a simple matrix type LCD, an excellent effect of improving display quality such as enlargement of a display area and reduction of crosstalk is exhibited.

[Brief description of the drawings]

FIG. 1A is a schematic cross-sectional view of an example of a three-layered transparent conductive substrate of the present invention, and FIG. 1B is a schematic cross-sectional view of an example of a five-layered transparent conductive substrate of the present invention.

FIG. 2 is a schematic cross-sectional view of a substrate for a color liquid crystal display used in the present invention.

FIG. 3 is a schematic cross-sectional view of an example of a transparent conductive substrate having a multilayer structure of an oxide layer of the present invention.

FIG. 4 is a schematic cross-sectional view of an example of a transparent conductive substrate in which an ITO film is formed on the air side of an uppermost oxide layer.

FIG. 5A is a schematic cross-sectional view of an example of a transparent conductive substrate in which another metal other than Ag is interposed at an interface between a metal layer containing Ag as a main component and an oxide layer of the present invention, and FIG. FIG. 4 is a schematic cross-sectional view of an example of a transparent conductive substrate in which a metal composition ratio other than Ag is high but a gradient composition metal film is used at an interface between a metal layer containing Ag as a main component and an oxide layer.

FIG. 6 (a) is a schematic cross-sectional view of an example of a transparent conductive substrate in which the metal layer of the present invention has a multilayer structure, and (b) the metal layer of the present invention is A
1 is a schematic cross-sectional view of an example of a transparent conductive substrate that is a graded metal film of a metal other than g and Ag.

FIG. 7 is a process schematic diagram of a patterning method according to the embodiment of the present invention.

8A is a schematic diagram of a TFT-type LCD electrode wiring according to a conventional example, and FIG. 8B is a schematic diagram of a TFT-type LCD electrode wiring according to an embodiment of the present invention.

[Explanation of symbols]

1: Base 2, 4, 6: Transparent oxide layer at least partially containing ZnO 3, 5: Film mainly composed of Ag 7: Color filter layer 8: Resin protective layer 9: Inorganic intermediate layer such as silica 10, 12: a transparent oxide layer mainly composed of In ₂ O ₃ 11: a transparent oxide layer mainly composed of ZnO 15, 17, 21: other metal layers other than Ag 16, 22: mainly composed of Ag Metal layers 18, 20, 23, 24: Metal layers other than Ag having a metal composition ratio of 50% or more 19: Metal layers having a composition ratio of Ag of 50% or more 26: Resist 27: Gate electrode 28: Gate Insulating film 29: Semiconductor layer 30: Pixel electrode (ITO) 31: Drain electrode 32: Source electrode 33: Drain electrode integrated with pixel electrode 34: Source electrode 39: Glass substrate

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yuki Kawamura Asahi Glass Co., Ltd., 1150 Hazawacho, Kanagawa-ku, Yokohama-shi, Kanagawa

Claims (12)

[Claims] 1. A transparent oxide layer and a metal layer are formed on a substrate in this order from a substrate side in a (2n + 1) layer (n is an integer of 1 or more).
In laminated with a transparent conductive film substrate comprising, a transparent oxide layer comprises ZnO and In ₂ O _3, the content of In ₂ O ₃ is 30 mol relative to the total amount of ZnO and In ₂ O ₃ % Or more, and the metal layer is a metal layer containing Ag. 2. The method according to claim 2, wherein the transparent oxide layer farthest from the substrate is In ₂
O ₃ has an In ₂ O ₃ rich layer formed of an oxide as the main component, the In ₂ O ₃ rich layer, 1) ZnO and In ₂
O ₃ and the total amount of ZnO and In ₂ O ₃
a layer in which n ₂ O ₃ is 90 mol% or more, 2) Sn-added I
a layer consisting only of n ₂ O ₃ (ITO) or 3) In ₂
2. The substrate with a transparent conductive film according to claim 1, which is a layer composed of only O ₃ . 3. A transparent oxide layer and a metal layer are laminated in five layers in this order, the fifth transparent oxide layer counted from the substrate side is composed of a lower layer and an upper layer, and the lower layer is composed of ZnO and In _2. and a O _3, the content of in ₂ O ₃ is, ZnO and in ₂ O ₃
An oxide layer is less than 30 mol% to 90 mol% relative to the total amount of the top layer, 1) a ZnO and In ₂ O _3, an In respect to the total amount of ZnO and In ₂ O _{3 2} O ₃
Is 90 mol% or more, 2) Sn-added In ₂ O <sub>3
3. The</sub> substrate with a transparent conductive film according to claim 1, which is a layer composed of only (ITO) or 3) a layer composed of only In ₂ O ₃ . 4. The first and third transparent oxide layers counted from the substrate side contain ZnO and In ₂ O ₃ , and contain In ₂ O ₃
4. The substrate with a transparent conductive film according to claim 3, wherein the content ratio of the oxide layer is 30 mol% or more and less than 90 mol% with respect to the total amount of ZnO and In ₂ O _{3. 5} . 5. The film thickness of the first transparent oxide layer counted from the substrate side is 10 to 50 nm, the film thickness of the third transparent oxide layer is 60 to 120 nm, and the fifth layer is The substrate with a transparent conductive film according to claim 3 or 4, wherein the thickness of the transparent oxide layer is 20 to 60 nm. 6. The substrate with a transparent conductive film according to claim 1, wherein the at least one metal layer is a layer made of an alloy film of Ag and another metal. 7. The substrate with a transparent conductive film according to claim 6, wherein the other metal is Au and / or Pd. 8. The substrate with a transparent conductive film according to claim 7, wherein the content ratio of Au and / or Pd in the metal layer is 0.1 to 5.0 atomic% based on the total amount with Ag. 9. The thickness of each metal layer is 3 to 20 nm.
The substrate with a transparent conductive film according to any one of claims 1 to 8, wherein 10. A method for producing a substrate with a transparent conductive film, comprising a substrate and a transparent oxide layer and a metal layer laminated in this order from the substrate side (2n + 1) layers (n is an integer of 1 or more). the transparent oxide layer comprises ZnO and in ₂ O _3, the content of in ₂ O ₃ forms a transparent oxide layer of more than 30 mol% based on the total amount of ZnO and in ₂ O _3,
A method for producing a substrate with a transparent conductive film, comprising forming a metal layer containing Ag as the metal layer. 11. A method of forming a (2n + 1) -layer transparent conductive film on a substrate, followed by heating to 100 to 300.degree.
The method for producing a substrate with a transparent conductive film according to the above. 12. A liquid crystal display device using the substrate with a transparent conductive film according to claim 1 as an electrode substrate.