JPH11174993A - Substrate with transparent conductive film and flat type display element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive film comprising a layered body of a silver layer and a dielectric layer for a display element, and to provide a transparent conductive film having chemical durability such as alkali resistance and hot moisture resistance and having processability into fine electrodes by acid etching. SOLUTION: This substrate 20 is substrate with a transparent conductive film comprising a transparent substrate 4 and a transparent conductive film 10 formed on the principal surface of the substrate. The transparent conductive film 10 is formed by alternately depositing dielectric layers 1 and metal layers 2 in this order form the substrate 4 side into (2n+1) layers ((n) is an integer of >=1). At least the outer surface of the dielectric layer 1 consists of a multiple oxide layer of indium and bismuth. The weight ratio of indium, bismuth and zinc composite oxide expressed in terms of metal oxides is preferably controlled to In2 O3 :Bi2 O3 :ZnO=(98 to 60):(1 to 40):(1 to 30).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate having a low-resistance transparent conductive film and a flat display element using the same, such as a liquid crystal display element, a plasma display element, an EL element, and an FED element. The present invention relates to a substrate with a transparent conductive film which is suitably used for a liquid crystal display device having an area, a high definition and a high speed response, and a liquid crystal display device using the same.

[0002]

2. Description of the Related Art Conventionally, as a substrate with a transparent conductive film used for a liquid crystal display device, a substrate in which tin-containing indium oxide (indium oxide doped with a small amount of tin: abbreviated as ITO) is coated on a glass substrate surface is used. ing. An ITO transparent conductive film obtained by etching an electrode pattern on a transparent electrode of a predetermined shape has excellent visible light transmittance,
Since the resistivity of the transparent conductive film has a large value of the order of 10 ⁻⁴ Ωcm, the thickness of the transparent electrode must be increased in order to increase the display area, to achieve high definition display, low crosstalk and high-speed response. Had to be made thicker.

In order to overcome this problem, Japanese Patent Laid-Open Publication No.
187399 and JP-A-7-114841 disclose an optical interference type low-resistance transparent conductive film in which ITO and silver are laminated.

Japanese Patent Application Laid-Open No. 7-325313 discloses a transparent conductive film employing a composite oxide of indium and zinc (abbreviated as IZO) as a dielectric layer laminated on a silver layer.

[0005]

The above-mentioned JP-A-63-1
The prior art laminated transparent conductive film composed of a laminate of a silver layer having a conductive function and an ITO layer having a protective function and a conductive auxiliary function disclosed in JP-A-87399 and JP-A-7-114481, Transparency (visible light transmittance)
And low resistance characteristics, but a dielectric layer (anti-reflection layer)
Although the ITO layer used as a display element has satisfactory alkali resistance as a display element application, the etching rate of the ITO layer with respect to acid is not sufficient as compared with the silver layer. There is a problem that the layer remains in the space portion of the pattern.

The transparent conductive film disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 7-325313 uses a composite oxide of indium and zinc as a dielectric layer laminated on a silver layer. Although the problems that occur during etching when ITO is used have been improved, there is a problem that the chemical resistance such as acid resistance and alkali resistance required for a display element is not sufficient.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and a transparent conductive film is not degraded in various steps when it is used for manufacturing a display element, and a display obtained is not deteriorated. It is an object of the present invention to provide a substrate with a transparent conductive film having characteristics necessary for ensuring the reliability of the device.

[0008]

The present invention provides a substrate with a transparent conductive film in which a transparent conductive film is coated on a main surface of a transparent substrate, wherein the transparent conductive film comprises a dielectric layer and a metal layer from the substrate side. (2n + 1) layers (n is an integer of 1 or more) alternately stacked in this order, and at least the outermost layer of the dielectric layer is a layer of a composite oxide of indium, bismuth, and zinc. It is a substrate with a transparent conductive film for an element.

By adding bismuth oxide to the indium oxide-zinc oxide binary system, the alkali resistance of the dielectric layer is significantly improved over the indium oxide-zinc oxide system without lowering the etching rate of the dielectric layer. He found that he could do that.

In the present invention, the number of repetitions of the alternating layers of the transparent conductive film is determined by the three-layer structure (n = 1) of the transparent substrate / first dielectric layer / metal layer / the outermost dielectric layer, The first dielectric layer / metal layer / second dielectric layer / metal layer / outermost dielectric layer (n = 2) can be used. In this case, at least the outermost layer is formed of indium, bismuth, and zinc. Of the composite oxide.

The composite oxide of indium, bismuth, and zinc (hereinafter abbreviated as IZBO) of the present invention is a compound formed by bonding indium, bismuth, zinc, and oxygen to a thermodynamically metastable amorphous state. In addition to the above, it may be in a stable crystalline state, and furthermore, indium oxide, bismuth oxide and zinc oxide may be present in the layer in a mere mixed state that is thermodynamically non-equilibrium.

The dielectric layer of the present invention is capable of processing electrodes (for example, hydrochloric acid) of a transparent conductive film while securing practically required durability for both acid resistance and alkali resistance, which are basic characteristics of chemical properties. (Etching with an acid containing), the content is preferably 60% by weight or more from the viewpoint of ensuring the solubility by the acid necessary for performing the etching.

In the present invention, bismuth oxide is 1% by weight.
It is preferable to contain the above from the viewpoint of increasing the etching rate of the dielectric layer by the acid and approaching that of the metal layer. More preferably, the dielectric layer is contained in an amount of 3% by weight or more in order to increase the function of protecting the dielectric layer itself against an alkaline atmosphere and thereby improve the alkali resistance of the transparent conductive film.

Further, the content of bismuth oxide is set to 40% by weight or less, from the viewpoint of suppressing the decrease in acid resistance of the dielectric layer, and further suppressing the deterioration of the conductivity from becoming significant, to 30% by weight or less. preferable.

When zinc oxide is contained in an amount of 1% by weight or more, the thin film of the dielectric layer becomes more amorphous and the film stress is reduced. As a result, the adhesion between the dielectric layer and the metal layer is increased, and the wet heat resistance of the transparent conductive film is improved. It is preferable to include zinc oxide in an amount of 5% by weight or more, because the wet heat resistance and the etching processability are further increased.

On the other hand, if zinc oxide is contained in an amount exceeding 30% by weight, the dielectric layer becomes weak to an alkaline atmosphere due to the reason that it is considered to be based on the chemical properties of zinc oxide itself, and the surface of the transparent conductive film becomes less conductive. It is not preferable because durability against alkali decreases.

As described above, at least the outermost composite oxide dielectric layer of the present invention is composed of indium oxide: bismuth oxide: zinc oxide = 98-60: 1 by weight% of metal oxide.
A ratio of 40: 1 to 30 is preferable in order to have a good balance between alkali resistance, etching processability with acid, and moist heat resistance.

The dielectric layer which is not the outermost surface in the present invention includes, in addition to a layer of a composite oxide of indium, bismuth and zinc, a layer of a composite oxide of indium and zinc, a layer of a composite oxide of indium and bismuth, Indium oxide, indium cerium oxide, indium titanium oxide, indium tin oxide (ITO), and a mixture thereof can be used. Each dielectric layer does not necessarily have to have the same composition. It is also possible to use those doped with aluminum, antimony, tin or the like for the purpose of improving the conductivity of the dielectric layer.

As the metal layer in the present invention, a silver layer is preferable because high transparency in the visible light region can be ensured. Further, in order to improve the chemical durability of the silver, such as the moisture and heat resistance, it is possible to contain a metal that forms a solid solution with the silver layer within a range that does not significantly reduce the transmittance.

The metal to be contained is effective in suppressing migration of silver by palladium and gold, which have characteristics of being easily dissolved in the silver layer and being stably dispersed, and palladium is effective in terms of similarity in optical characteristics and etching characteristics. Most preferred.
The amount is 0.1 palladium based on all metals.
Preferably, the content of gold is 0.1 to 3 atomic%, and the content of gold is 0.1 to 3 atomic%.

When both palladium and gold are contained at less than 0.1 atomic%, the effect of improving the chemical durability is small, and when more than 3 atomic%, the visible light transmittance of the transparent conductive film is reduced. This is not preferable because it makes it difficult to obtain a bright display element.

When the metal layer of the transparent conductive film of the present invention is composed of two or more layers, the metal layer is mainly composed of silver in order to make the vertical visible light transmittance of the whole substrate with the transparent conductive film 70% or more. It is preferable that the total thickness of the film is 100 nm or less.

In the present invention, when the metal layer is a layer containing silver as a main component, the silver main component layer is in contact with a side far from the substrate, and is made of palladium, gold, zinc, titanium, copper, nickel, platinum or iron. 5 nm thick second metal layer containing any one as a main component
By interposing with the following thickness, it is possible to prevent the silver from being oxidized and deteriorated which may occur when the dielectric layer is coated on the silver main layer.

Examples of the transparent substrate that can be used in the present invention include well-known glass substrates such as soda-lime-silica glass and borosilicate glass (alkali-free glass), as well as polyethylene terephthalate (PET) and acrylic (PMMA). Plastic substrates and plastic films, and substrates provided with a color filter for color display on the surface of these substrates. Also, these substrates need not be flat,
A substrate having a certain kind of curved surface or unevenness may be used.

As the color filter, a known color filter in which organic dyes and organic pigments are arranged in stripes or the like by photolithography using polyimide, acrylic resin, photosensitive resin or the like as a base material can be used. An organic resin flattening film is provided on the color filter, and in some cases, between the dielectric layer and the organic resin film,
An adhesion promoting layer of an inorganic oxide such as silicon dioxide can be provided.

The two substrates with a transparent conductive film are bonded to each other with an adhesive so that the transparent conductive films face each other with an adhesive to form a sealed space between the substrates, and a liquid crystal is sealed in the sealed space. When manufacturing a known liquid crystal display element, an active liquid crystal display element in which a high-definition and bright STN or TN type liquid crystal display element or a TFT or the like is arranged by using at least one of the substrates with a transparent conductive film of the present invention. It can be.

The dielectric layer and the metal layer of the present invention can be formed by a known method of forming a vacuum thin film such as sputtering, vacuum deposition, or ion plating. For example, a composite oxide of indium, bismuth, and zinc can be formed by sputtering a fine powder sintered body of indium oxide, bismuth oxide, and zinc oxide, or reacting an alloy or mixture of indium metal, bismuth metal, and zinc metal with oxygen. The film can be formed by sputtering.

Film formation can be carried out usually at room temperature, and may be carried out while heating the substrate at a temperature of about 300 ° C. or less in order to improve the crystallinity of silver. After the film is formed at room temperature, the obtained laminated film is heated to a temperature of about 300 ° C. or
By performing the heat treatment at a temperature at which the layer of the organic resin such as the color filter does not deteriorate, the specific resistance and the transmittance of the silver layer can be improved, and the protection performance of the dielectric layer can be improved.

[0029]

FIG. 1 is a sectional view of an embodiment of the present invention.
Shown in The substrate 20 with a transparent conductive film is formed by coating a transparent conductive film 10 on a glass substrate 4.
Numeral 0 indicates a composite oxide layer 1 of indium oxide, bismuth oxide and zinc oxide, a palladium-containing silver layer 2, a titanium layer 3, and a composite oxide layer 1 of indium oxide, bismuth oxide and zinc oxide laminated in this order. .

FIG. 2 is a sectional view of another embodiment of the present invention. In the substrate 20 with a transparent conductive film, a transparent conductive film 10 is coated on a glass substrate 4, and this transparent conductive film 10 is composed of a composite oxide layer 1 of indium oxide, bismuth oxide and zinc oxide and a palladium-containing silver layer. 2 is composed of five layers alternately stacked.

FIG. 3 shows an embodiment of the flat display element of the present invention.
Shown in A color filter 30 of three primary colors of RGB is provided on one surface of the upper glass substrate 4, and the color filter 30 is covered with a protective film 50 made of an organic resin. The electrode is processed and covered. The transparent conductive film is formed on the surface of the lower glass substrate 4 with the transparent conductive film 10 on the upper side so that the direction of the stripe-shaped electrode is orthogonal to the transparent conductive film 10.

The liquid crystal alignment film 60 including the transparent conductive film 10
Is applied, and the liquid crystal is sealed in a sealing material (not shown) formed between the two substrates. A voltage is applied between the transparent conductive films 10 and 10.

The sheet resistance is about 1.0-2.5Ω / □,
As an embodiment of a substrate with a transparent conductive film having a characteristic of visible light transmittance of 60% or more, a glass plate / IZBO layer (In ₂ O ₃ : ZnO: Bi ₂ O ₃ = 80: 5: 1 by weight%)
5) Metal layer of 20 to 80 nm / 99.5 atomic% of silver / 0.5 atomic% of palladium 5 to 30 nm / IZBO layer (same as above) 50 to 120 nm / metal of 99.5 atomic% of silver / 0.5 atomic% of palladium A laminated structure of 5 to 30 nm / IZBO layer (same as above) and 20 to 80 nm is exemplified.

Further, in order to obtain a substrate with a transparent conductive film having a visible light transmittance of 65% or more when the sheet resistance is 1.5Ω / □ or less, a glass plate / IZBO layer (In ₂ O by weight%) is required. ₃ : ZnO: Bi ₂ O ₃ = 70: 15: 15) 20
-80 nm / metal layer of 99.5 atomic% of silver-0.5 atomic% of palladium 5-30 nm / IZBO layer (same as above) 50-1
20 nm / 99.5 atomic% of silver-0.5 atomic% of palladium
Metal layer 5 to 30 nm / IZBO layer (same as above) 50 to 12
0 nm / silver 99.5 atom% -palladium 0.5 atom% metal layer 5-30 nm / IZBO layer (same as above) 20-80 n
m and the like.

Moisture / heat resistance evaluated by exposure to air under high temperature and high humidity conditions for a certain period of time, transparency evaluated by high visible light transmittance including substrate, and electrical characteristics evaluated by low sheet resistance The evaluation criteria for the electrode's etching processability and alkali resistance, which are evaluated based on the ease of etching and its uniformity, are as follows. Moisture / heat resistance: Good for 1000 hours or more in a microscopic inspection of a constant temperature and high humidity test without occurrence of silver aggregation. : Good, without silver aggregation, etc., for up to 500 hours in a microscopic inspection of a constant temperature and high humidity test. X: Aggregation of silver or the like occurs in 25 to 100 hours. XX: Aggregation of silver occurs within 24 hours or less. Etching processability ：: Stripe-shaped electrodes having an electrode width / electrode distance of 30/10 μm can be etched well. : Stripe-shaped electrodes having an electrode width / inter-electrode distance of 50/15 μm can be favorably etched. ×: Stripe-shaped electrodes having an electrode width / inter-electrode distance of 50/15 μm could not be etched. Alkali resistance A: NaOH 3% No turbidity on film surface at 60 ° C for 3 minutes or more. : No white turbidity on the film surface for 2 minutes or more at 60% of NaOH 3%. X: NaOH 3% The film surface becomes cloudy within 1 minute at 60 ° C. XX: NaOH 3% The film surface becomes cloudy within 30 seconds at 60 ° C.

The terms used in Tables 1 and 2 are described below. Film structure: The left side is the substrate side. Transmittance: wavelength 525nm including soda lime glass substrate
Value. Moisture and heat resistance: results of a constant temperature and humidity test at 90% RH and 60 ° C. IZBO: Short for composite oxide of indium, bismuth and zinc. IZO: Short for composite oxide of indium and zinc. IBO: short for composite oxide of indium and bismuth. Heat treatment: in air at 230 ° C. for 30 minutes.

Hereinafter, the present invention will be described with reference to examples. Example 1 After washing a glass substrate of soda lime silica composition for simple matrix liquid crystal display having a length of 400 mm, a width of 300 mm and a thickness of 0.7 mm, a silicon dioxide layer for alkali passivation was formed to a thickness of 30 nm. Next, as a sputtering target, using a target for a dielectric layer of indium bismuth zinc oxide (IZBO) in which the oxide weight% of bismuth oxide, zinc oxide and indium oxide is 15: 7: 78 weight%, and a silver target, (DC) IZBO layer / metal layer / IZBO layer / metal layer /
The IZBO layer was formed to a thickness of 40 nm, 18 nm, 8
The sample was coated on a glass substrate in the order of 5 nm, 19 nm, and 39 nm to obtain a glass sample 1 with a transparent conductive film. Further, the transparent conductive film of Sample 1 was formed into a striped transparent electrode having an electrode width of 30 μm and an electrode interval of 10 μm,
The electrode pattern was etched using an etching solution composed of an aqueous solution containing hydrochloric acid and nitric acid. Table 1 shows the characteristics of Sample 1.

Example 2 After washing a glass substrate of soda lime silica composition for a simple matrix liquid crystal display having a length of 400 mm, a width of 300 mm and a thickness of 0.7 mm, a silicon dioxide layer for alkali passivation of 30 nm was formed. Next, as a sputtering target, a target for a dielectric layer of indium-bismuth-zinc-oxide (IZBO) having an oxide weight percentage of zinc oxide, bismuth oxide, and indium oxide of 5: 4: 91 and silver 9
IZBO layer / metal layer (99.5 atomic% of silver, 0.5% of palladium
Atomic%) / IZBO layer / metal layer / I
The ZBO layer was formed to a thickness of 39 nm, 18 nm, 84
The glass was sequentially coated on a glass substrate so as to have a thickness of nm, 18 nm, and 41 nm to obtain a sample 2 of glass with a transparent conductive film.
Further, the transparent conductive film of Sample 2 was etched with an etching solution composed of an aqueous solution containing hydrochloric acid and nitric acid so as to form a striped transparent electrode having an electrode width of 50 μm and an electrode interval of 15 μm. Table 1 shows the characteristics of Sample 2.

Example 3 After washing a glass substrate of soda lime silica composition with a color filter for a simple matrix liquid crystal display having a length of 420 mm, a width of 300 mm and a thickness of 0.7 mm, bismuth oxide, zinc oxide and indium oxide were used as sputtering targets. IZB by DC sputtering using a mixture target of indium oxide, bismuth oxide, and zinc oxide having a weight percentage of 30:20:50 and a metal layer target of 99.6 atomic percent silver and 0.4 atomic percent palladium.
Each of the O layer / metal layer / IZBO layer / metal layer / IZBO layer has a thickness of 38 nm, 17 nm, 84 nm, and 20 n.
m and 41 nm were sequentially coated on a glass substrate to obtain a glass sample 3 with a transparent conductive film. At this time, the substrate was heated at 220 ° C. during film formation in a sputtering apparatus, and the resistance of the film when not heated was improved by about 40%. Further, the transparent conductive film of Sample 3 was formed into a striped transparent electrode having an electrode width of 30 μm and an electrode interval of 10 μm.
The electrode pattern was etched using an etching solution composed of an aqueous solution containing hydrochloric acid and nitric acid. Table 1 shows the characteristics of Sample 3.

Examples 4 to 6 Samples were prepared using the same glass plate and film forming method as in Example 1 by changing the composition and thickness of the dielectric layer, the sputtering target using the composition and thickness of the metal layer, and the film forming time. 4 to 6 were produced.

[0041]

[Table 1]

Comparative Example 1 After washing a glass substrate of soda lime silica composition for simple matrix liquid crystal display having a length of 400 mm, a width of 300 mm and a thickness of 0.7 mm, a silicon dioxide layer for alkali passivation of 30 nm was formed. Next, using a metal containing indium oxide containing 10% of zinc oxide and 99.5% by weight of silver and 0.5% by weight of palladium as a sputtering target by DC sputtering, IZO.
Layer / metal layer (consisting of a composition of approximately 99.5% by weight of silver and 0.5% by weight of palladium by film analysis) / IZO layer / metal layer / IZO layer in a thickness of 45 nm and 19n, respectively.
m, 90 nm, 19 nm, and 43 nm were sequentially coated on a glass substrate to obtain Comparative Sample 1 of glass with a transparent conductive film. In addition, the transparent conductive film of Comparative Sample 1 was etched with an etching solution composed of an aqueous solution containing hydrochloric acid so that a striped transparent electrode having an electrode width of 50 μm and an electrode interval of 15 μm was formed. Table 2 shows the characteristics of Comparative Sample 1.

Comparative Example 2 After washing a glass substrate of soda lime silica composition for a simple matrix liquid crystal display having a length of 400 mm, a width of 300 mm and a thickness of 0.7 mm, a silicon dioxide layer for alkali passivation of 30 nm was formed. Next, using an indium oxide containing 10% tin oxide and a metal containing 99% by weight of silver and 1% by weight of palladium as a sputtering target, an ITO layer / metal layer (substantially 99% silver by film analysis) was used by a DC sputtering method. % Palladium 1% by weight) / ITO layer / metal layer / ITO layer in a thickness of 41 nm, 19 nm, 81 nm, 1 nm, respectively.
The glass was sequentially coated on the glass substrate so as to have a thickness of 8 nm and a thickness of 39 nm, thereby obtaining Comparative Sample 2 of a glass with a transparent conductive film. The electrode pattern was etched with an etching solution containing an aqueous solution containing hydrochloric acid so that the transparent conductive film of Comparative Sample 2 became a striped transparent electrode having an electrode width of 50 μm and an electrode interval of 15 μm. Then 230 ℃ in the air
Heat treatment was performed for 30 minutes to improve the resistance value of the film by about 20%. Table 2 shows the characteristics of Comparative Sample 2.

[0044]

[Table 2]

Tables 1 and 2 show the obtained samples 1 to
6 and Comparative Samples 1 and 2 obtained in Comparative Examples, the sheet resistance, transmittance, wet heat resistance, etching processability, and alkali resistance are collectively shown. From these tables, it can be seen that Samples 1 to 6 of Examples in which the outermost dielectric layer is a composite oxide of indium, bismuth and zinc have good wet heat resistance and alkali resistance, and have a high definition of 15 μm. It can be seen that the substrate has a low-resistance transparent conductive film that can be processed into an electrode having a required inter-electrode distance. In particular, it can be seen that Example 3 contains bismuth oxide in a relatively large amount, and thus has particularly excellent alkali resistance in addition to etching processability.

Comparative Sample 1 does not contain bismuth oxide in the outermost dielectric layer, and therefore has extremely poor alkaline properties as compared with wet heat resistance and etching processability.
It can be seen that the characteristics are not retained in a well-balanced manner. Sample 2 of the comparative example using indium oxide as the dielectric layer is:
On the contrary, although the alkali resistance was excellent, the wet heat resistance and the etching processability were not sufficient, and it was found that these three properties were not well-balanced.

[0047]

According to the present invention, at least the dielectric layer on the outermost surface of the transparent conductive film is protected with a layer of a composite oxide of indium, bismuth and zinc. , And a substrate with a transparent conductive film having characteristics capable of processing fine electrodes. By using the substrate with a transparent conductive film of the present invention, a liquid crystal display device having excellent reliability can be obtained.

Further, by setting the ratio of indium oxide, bismuth oxide and zinc oxide in the dielectric layer within a predetermined range, a good balance between alkali resistance, wet heat resistance and etching workability capable of processing fine electrodes is obtained. A substrate with a transparent conductive film can be obtained.

Further, since the transparent conductive film of the present invention is mainly composed of a thin-film metal for the layer mainly having conductivity, the resistance can be made low. Further, by using silver as the metal layer, it is possible to increase the visible light. The transmittance can be set. Thus, a transmissive display used in combination with a backlight can be a bright display element.

Further, by adding palladium or gold in a predetermined amount range to silver, a transparent conductive film having improved moist heat resistance and alkali resistance can be obtained, whereby a display element having excellent durability reliability can be obtained. It can be.

According to the present invention, in which a color filter for color display is interposed between a transparent substrate and a transparent conductive film, a metal layer or a dielectric layer is formed on the color filter without heating the transparent substrate. Therefore, the color characteristics of the color filter made of an organic resin are not deteriorated by heat.
Thus, a substrate with a low-resistance transparent conductive film for color display having good color characteristics can be obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of one embodiment of a substrate with a transparent conductive film of the present invention.

FIG. 2 is a sectional view of another embodiment of the substrate with a transparent conductive film of the present invention.

FIG. 3 is a schematic cross-sectional view of a liquid crystal display device manufactured using the substrate with a transparent conductive film of the present invention.

[Explanation of symbols]

1: composite oxide layer of indium oxide, bismuth oxide and zinc oxide, 2: palladium-containing silver layer, 3: titanium layer, 4: glass substrate, 10: transparent conductive film, 20: substrate with transparent conductive film, 30 : Color filter, 40: liquid crystal layer, 50: protective film, 60: alignment film,

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01J 5/08 H01J 5/08 H05B 33/28 H05B 33/28

Claims (6)

[Claims] 1. In a substrate with a transparent conductive film in which a transparent conductive film is coated on a main surface of a transparent substrate, the transparent conductive film is formed by alternately forming a dielectric layer and a metal layer in this order from the substrate side (2n + 1). Layers (n is an integer of 1 or more) laminated,
A substrate with a transparent conductive film for a display element, wherein at least the outermost layer of the dielectric layer is a layer of a composite oxide of indium, bismuth and zinc. 2. The metal oxide-equivalent weight ratio of a layer of a composite oxide of indium, bismuth, and zinc according to claim 1,
In ₂ O ₃ : Bi ₂ O ₃ : ZnO = 98 to 60: 1 to 40:
Substrate with a transparent conductive film for a display element which is 1 to 30. 3. The substrate with a conductive film for a display element according to claim 1, wherein the metal layer is a layer containing silver as a main component. 4. The method according to claim 3, wherein the metal layer is at least one selected from the group consisting of silver, palladium and gold.
A substrate with a transparent conductive film for a display element, which contains 0.1 to 3 atomic% of the total metal amount. 5. The method according to claim 1, wherein
A substrate with a transparent conductive film for a color display element, wherein a color filter is provided between the transparent substrate and the transparent conductive film. 6. A substrate with a transparent conductive film for a display element according to claim 1, wherein at least one of the substrates is a transparent substrate, and a sealed space is provided between the substrate and the other substrate disposed opposite to the transparent substrate. The formed flat display element.