WO2015125558A1

WO2015125558A1 - Method for manufacturing transparent electroconductive body and electroconductive body

Info

Publication number: WO2015125558A1
Application number: PCT/JP2015/051985
Authority: WO
Inventors: 智一田口; 一成多田; 仁一粕谷
Original assignee: コニカミノルタ株式会社
Priority date: 2014-02-20
Filing date: 2015-01-26
Publication date: 2015-08-27
Also published as: JPWO2015125558A1

Abstract

　The purpose of the present invention is to provide a method for manufacturing a transparent electroconductive body, and an electroconductive body in which light absorption is reduced, reflection of light in the visible light region is prevented, and resistivity is low. A method for manufacturing a transparent electroconductive body (10) having at least, in this order, a transparent substrate (1), a first high-refractive-index layer (2), a transparent metal layer (3), and a second high-refractive-index layer (4) by the roll-to-roll method, the method for manufacturing a transparent electroconductive body being characterized in having a step for forming the transparent metal layer (3) while the temperature of the transparent substrate (1) is kept at 65°C or less.

Description

Method for producing transparent conductor and transparent conductor

The present invention relates to a method for producing a transparent conductor and a transparent conductor. More specifically, the present invention relates to a method of manufacturing a transparent conductor with reduced light absorption, which prevents reflection of light in the visible light region, and has low resistance.

In recent years, transparent conductive films have been used in various devices such as liquid crystal displays, plasma displays, inorganic and organic EL (electroluminescence) displays, touch panels, and solar cells.

As a material constituting such a transparent conductive film, gold (Au), silver (Ag), platinum (Pt), copper (Cu), rhodium (Rh), palladium (Pd), aluminum (Al), chromium (Cr ) And other oxide semiconductors such as In ₂ O ₃ , CdO, CdIn ₂ O ₄ , Cd ₂ SnO ₄ , TiO ₂ , SnO ₂ , ZnO, and ITO (Indium Tin Oxide) are known.

Here, in a touch panel type display device or the like, a wiring made of a transparent conductive film or the like is disposed on the image display surface of the display element. Therefore, the transparent conductive film is required to have high light transmittance. In such various display devices, a transparent conductive film made of ITO having high light transmittance is often used.

In recent years, a capacitive touch panel display device has been developed, and it is required to further reduce the surface electrical resistance of the transparent conductive film. However, the conventional ITO film has a problem that the surface electrical resistance cannot be lowered sufficiently.

Therefore, it has been studied to use a vapor-deposited film of Ag as a transparent conductive film (see Patent Document 1). In order to increase the light transmittance of the transparent conductor, an Ag layer made of an Ag film is formed of a layer having a high refractive index (for example, niobium oxide (Nb ₂ O ₅ ), IZO (Indium Zinc Oxide), ICO (Indium Cerium Oxide)). Further, it is also proposed to sandwich the layer between a-GIO (amorphous Gallium Indium Oxide), a layer made of zinc oxide, ITO, or the like (see Patent Documents 2 to 6 and Non-Patent Document 3). Further, it has also been proposed to sandwich the Ag layer with a zinc sulfide (ZnS) layer (see Non-Patent Documents 1 and 2).

However, as shown in Patent Documents 2 to 4, a transparent conductor in which an Ag layer is sandwiched between dielectric layers such as niobium oxide and IZO has insufficient moisture resistance. As a result, when a transparent conductor is used in a high humidity environment, there is a problem that the Ag layer is easily corroded.

Further, in the transparent conductor in which the Ag layer is sandwiched between the ZnS layers, the moisture resistance of the transparent conductor is sufficiently high, but Ag is sulfided to form silver sulfide when the Ag layer is formed or when the ZnS layer is formed. Cheap. As a result, there is a problem that the light transmittance of the transparent conductor is lowered.

Also, the transparent conductive films described in Patent Documents 5 and 6 have a problem that the light absorption (film absorption) by the transparent metal layer is large, and as a result, the light transmittance is insufficient.

Special table 2011-508400 gazette JP 2006-184849 A JP 2002-15623 A JP 2008-226581 A JP 2010-157497 A JP 2001-249221 A

The present invention has been made in view of the above problems and situations, and a solution to that problem is a method of manufacturing a low-resistance transparent conductor in which light absorption is reduced and reflection of light in the visible light region is prevented. And providing a transparent conductor.

A transparent metal layer is formed while keeping the temperature of the transparent substrate at a low temperature, and the high refractive index layer contains a dielectric material or an oxide semiconductor material having a refractive index larger than that of the transparent substrate. One layer is formed as a zinc sulfide-containing layer containing zinc sulfide (ZnS), and a layer containing at least a specific metal compound or metal is formed between the transparent metal layer and the zinc sulfide-containing layer. Therefore, the uppermost layer (the layer opposite to the transparent substrate) can be made conductive to prevent sulfidation of the transparent metal layer while ensuring low resistance and moisture resistance. Furthermore, the transparent metal layer absorbs light. It has been found that a method for producing a transparent conductor capable of reducing (film absorption) can be obtained, and the present invention has been achieved.
That is, the said subject which concerns on this invention is solved by the following means.

1. A transparent conductor manufacturing method for manufacturing a transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order by a roll-to-roll method,
A method for producing a transparent conductor, comprising the step of forming the transparent metal layer while maintaining the temperature of the transparent substrate at 65 ° C. or lower.

2. A dielectric material or an oxide semiconductor material having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm, and one of the first high refractive index layer and the second high refractive index layer The method of claim 1, further comprising the step of forming the first high refractive index layer and the second high refractive index layer as a zinc sulfide-containing layer containing zinc sulfide (ZnS). A method for producing a transparent conductor.

3. The method further includes the step of forming an anti-sulfurization layer containing at least one selected from metal oxides, metal fluorides, metal nitrides, and zinc (Zn) between the transparent metal layer and the zinc sulfide-containing layer. The method for producing a transparent conductor according to item 2, wherein:

4. The step of forming the sulfidation preventive layer comprises the step of forming the sulfidation layer containing the metal oxide under a vacuum and an atmospheric condition in which oxygen gas is not introduced on the surface of the transparent metal layer opposite to the transparent substrate. 4. The method for producing a transparent conductor according to item 3, which is a step of forming a layer.

5. 5. The transparent conductor according to any one of items 1 to 4, wherein a formation rate when forming the transparent metal layer is 0.3 nm / s (3 Å / s) or more. Manufacturing method.

6. The method for producing a transparent conductor according to any one of items 1 to 5, wherein krypton or xenon is used as a sputtering gas in the step of forming the transparent metal layer.

7). A transparent conductor manufactured by the method for manufacturing a transparent conductor according to any one of items 1 to 6,
The first high refractive index layer and the second high refractive index layer contain a dielectric material or an oxide semiconductor material having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm, and One of the high refractive index layer and the second high refractive index layer is a zinc sulfide-containing layer containing zinc sulfide (ZnS), and
Between the transparent metal layer and the zinc sulfide-containing layer, an antisulfurization layer containing at least one selected from metal oxides, metal fluorides, metal nitrides, and zinc (Zn) is provided. Transparent conductor.

8. 8. The transparent conductor according to item 7, wherein the anti-sulfurization layer contains zinc oxide (ZnO) as at least the metal oxide.

By the above means of the present invention, it is possible to provide a method and a transparent conductor for producing a low-resistance transparent conductor in which light absorption is reduced and reflection of light in the visible light region is prevented.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

When the transparent substrate is at a high temperature, particles constituting a transparent metal layer (here, metal particles such as silver particles) that have reached the layer opposite to the transparent substrate (here, referred to as a sulfidation prevention layer) are used. Has a high thermal energy, and is easy to move on the surface of the sulfidation prevention layer. As a result, the metal particles easily aggregate with each other, form a surface of a so-called island structure (island state), and easily induce plasmon absorption, thereby exhibiting large light absorption.
On the other hand, when the transparent substrate is at a low temperature, it is presumed that the metal particles that have reached the anti-sulfurization layer do not move much on the surface of the anti-sulfurization layer because of low thermal energy. As a result, since each metal particle does not move, it does not aggregate, thus forming a continuous film-like surface without taking an island-like structure, and thus exhibiting less light absorption because it does not induce plasmon absorption. .

Schematic sectional view showing an example of the layer structure of a transparent conductor Schematic sectional view showing another example of layer structure of transparent conductor Schematic diagram showing an example of a pattern composed of a conductive region and an insulating region of a transparent conductor Schematic configuration diagram showing a transparent conductor manufacturing device Schematic configuration diagram showing an example of a forming chamber constituting a transparent conductor manufacturing apparatus Schematic showing a part of transparent substrate Graph showing admittance locus in an example of transparent conductor A graph showing the relationship between the temperature of the transparent substrate and the light absorption rate when forming the transparent metal layer A graph showing the formation rate and light absorption rate when forming a transparent metal layer

The transparent conductor manufacturing method of the present invention is a transparent conductor that has at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order by a roll-to-roll method. A method for producing a conductor, comprising a step of forming a transparent metal layer while maintaining a temperature of the transparent substrate at 65 ° C. or lower. This feature is a technical feature common to the inventions according to claims 1 to 8.

As an embodiment of the present invention, from the viewpoint of manifestation of the effect of the present invention, it contains a dielectric material or an oxide semiconductor material having a refractive index larger than that of a transparent substrate with respect to light having a wavelength of 570 nm, A step of forming the first high refractive index layer and the second high refractive index layer by using any one of the refractive index layer and the second high refractive index layer as a zinc sulfide-containing layer containing zinc sulfide (ZnS); It is preferable to have it because moisture can be prevented from permeating from the transparent substrate side, and thus corrosion of the transparent metal layer can be suppressed.

In the present invention, a step of forming an antisulfurization layer containing at least one selected from metal oxides, metal fluorides, metal nitrides, and zinc (Zn) between the transparent metal layer and the zinc sulfide-containing layer. Further, it is preferable that the transparent metal layer can be prevented from being sulfided and, consequently, the light transmittance can be improved.

In the present invention, it is preferable that the formation speed (film formation speed) when forming the transparent metal layer is 0.3 nm / s (3 Å / s) or more. Thus, by ensuring a high formation rate, light absorption (film absorption) by the transparent metal layer can be reduced, and further, the sheet resistance value can be reduced.

Further, in the present invention, the step of forming the anti-sulfurization layer comprises the step of forming the metal oxide under a vacuum and an atmospheric condition in which oxygen gas is not introduced on the surface of the transparent metal layer opposite to the transparent substrate. It is preferable to be a step of forming the sulfidation preventive layer containing matter. Thereby, it can suppress that oxygen plasma reacts with a transparent metal layer, the said transparent metal layer surface is roughened, and can reduce light absorption by extension.

In the present invention, it is preferable to use a heavy rare gas such as krypton or xenon as the sputtering gas in the step of forming the transparent metal layer because a transparent conductor with less light absorption can be obtained.

Furthermore, as the transparent conductor of the present invention, the first high-refractive index layer and the second high-refractive index layer have a higher refractive index than that of the transparent substrate with respect to light having a wavelength of 570 nm, or an oxidation material. A zinc sulfide-containing layer containing zinc sulfide (ZnS), wherein one of the first high-refractive index layer and the second high-refractive index layer is a zinc sulfide-containing layer. It is characterized by having an antisulfurization layer containing at least one selected from metal oxide, metal fluoride, metal nitride and zinc (Zn) between the metal layer and the zinc sulfide-containing layer. preferable. Thereby, light absorption is reduced, reflection of light in the visible light region is prevented, and a low-resistance transparent conductor can be provided.

Furthermore, as the transparent conductor of the present invention, it is preferable that the sulfidation prevention layer contains at least zinc oxide (ZnO) as the metal oxide. Thereby, the sulfidation of the transparent metal layer can be prevented, and the light transmittance can be improved.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[Outline of transparent conductor]
Examples of the layer structure of the transparent conductor according to the present invention are shown in FIGS. As shown in FIGS. 1 and 2, the transparent conductor 10 according to the present invention includes a transparent substrate 1 / first high refractive index layer 2 / transparent metal layer 3 / second high refractive index layer 4. In the transparent conductor 10 according to the present invention, either or both of the first high refractive index layer 2 and the second high refractive index layer 4 are zinc sulfide-containing layers containing zinc sulfide (ZnS). . Between the zinc sulfide-containing

layers

2 and 4 and the transparent metal layer 3, an antisulfurization layer 5 (5a and 5b) is included.

Here, when one of the first high refractive index layer 2 and the second high refractive index layer 4 is a zinc sulfide-containing layer, the first high refractive index layer 2 or the second high refractive index layer 2 that is a zinc sulfide-containing layer. Between the refractive index layer 4 (hereinafter also referred to as “zinc sulfide-containing

layer

2 or 4”) and the transparent metal layer 3, an antisulfurization layer 5 is included. On the other hand, when both the first high-refractive index layer 2 and the second high-refractive index layer 4 are zinc sulfide-containing layers, the sulfide is interposed between any one of the zinc sulfide-containing

layers

2 or 4 and the transparent metal layer 3. The prevention layer 5 may be included, but from the viewpoint of sufficiently increasing the light transmittance of the transparent conductor 10, the sulfide prevention layer 5 is provided between each of the zinc sulfide-containing

layers

2 and 4 and the transparent metal layer 3. Is preferably included. That is, it is preferable that the antisulfurization layer 5 is included between the first high refractive index layer 2 and the transparent metal layer 3 and between the transparent metal layer 3 and the second high refractive index layer 4.

When the transparent metal layer and the layer containing zinc sulfide (ZnS) are formed adjacent to each other, there is a problem that metal sulfide is easily generated and the light transmittance of the transparent conductor is easily reduced. The metal sulfide is presumed to be produced as follows.

When a transparent metal layer is formed on a zinc sulfide-containing layer (first high refractive index layer) by a vapor deposition method such as sputtering, the unreacted sulfur component in the zinc sulfide-containing layer is a material of the transparent metal layer. Repelled into the forming atmosphere by (metal material). Then, the ejected sulfur component reacts with the metal derived from the transparent metal layer, and metal sulfide is deposited on the zinc sulfide-containing layer. Further, when the zinc sulfide-containing layer and the transparent metal layer are continuously formed, the sulfur component contained in the atmosphere in which the zinc sulfide-containing layer is formed remains in the transparent metal layer atmosphere. And this sulfur component and the metal derived from a transparent metal layer react, and metal sulfide deposits on a zinc sulfide content layer.

On the other hand, when the zinc sulfide-containing layer (second high refractive index layer) is formed on the transparent metal layer, the metal in the transparent metal layer is expelled into the forming atmosphere by the material of the zinc sulfide-containing layer. The ejected metal reacts with the sulfur component, and metal sulfide is deposited on the surface of the transparent metal layer. Furthermore, a metal sulfide is generated on the surface of the transparent metal layer also when the surface of the transparent metal layer comes into contact with the sulfur component in the forming atmosphere.

On the other hand, in the transparent conductor 10 according to the embodiment of the present invention, for example, as shown in FIG. 1, the first antisulfurization layer 5 a is laminated on the first high refractive index layer 2. In such a configuration, since the first high refractive index layer 2 is protected by the first antisulfurization layer 5a, it is possible to prevent the sulfur component in the first high refractive index layer 2 from being ejected when the transparent metal layer 3 is formed. it can. Even if the transparent metal layer 3 is continuously formed (deposited) from the first high refractive index layer 2, the sulfur component contained in the atmosphere in which the first high refractive index layer 2 is formed becomes the first antisulfurization layer 5 a. Or adsorbed to the constituents of the first antisulfurization layer 5a. Therefore, it can suppress that sulfur is contained in the formation atmosphere of the transparent metal layer 3, and the production | generation of a metal sulfide can be avoided.

In the transparent conductor 10 according to the embodiment of the present invention, for example, as shown in FIG. 1, the second antisulfurization layer 5 b is laminated on the transparent metal layer 3. In such a configuration, since the transparent metal layer 3 is protected by the second antisulfurization layer 5b, it is possible to suppress the metal in the transparent metal layer 3 from being ejected when the second high refractive index layer 4 is formed. Further, it is possible to prevent the sulfur component in the atmosphere in which the second high refractive index layer 4 is formed from coming into contact with the surface of the transparent metal layer 3. Therefore, generation of metal sulfide on the surface of the transparent metal layer 3 can be avoided.

In the transparent conductor 10 according to the embodiment of the present invention, the transparent metal layer 3 may be laminated on the entire surface of the transparent substrate 1 as shown in FIG. 1, and the transparent metal layer 3 as shown in FIG. 2. May be patterned into a desired shape. In the transparent conductor according to the embodiment of the present invention, the region a where the transparent metal layer 3 is laminated is a region where electricity is conducted (hereinafter also referred to as “conduction region”). On the other hand, as shown in FIG. 2, the region b where the transparent metal layer 3 is not included is an insulating region.

The pattern composed of the conductive region a and the insulating region b is appropriately selected according to the use of the transparent conductor 10. For example, when the transparent conductor 10 is applied to an electrostatic touch panel, as shown in FIG. 3, the pattern includes a plurality of conductive regions a and line-shaped insulating regions b that divide the conductive regions a. sell.

Further, the transparent conductor 10 according to the present invention may include layers other than the transparent substrate 1, the first high refractive index layer 2, the transparent metal layer 3, the second high refractive index layer 4, and the antisulfurization layer 5. Good. For example, an underlayer that can be a growth nucleus when forming the transparent metal layer 3 may be included between the transparent metal layer 3 and the first high refractive index layer 2 adjacent to the transparent metal layer 3. However, the layers included in the transparent conductor 10 according to the present invention are all layers made of an inorganic material except for the transparent substrate 1. For example, even if an adhesive layer made of an organic resin is laminated on the second high refractive index layer 4, the laminated body from the transparent substrate 1 to the second high refractive index layer 4 is the transparent conductor 10 according to the present invention. is there.

(Method for producing transparent conductor of the present invention)
The method for producing a transparent electrode according to the present invention includes a transparent conductive material comprising a transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order by a roll-to-roll method. It is a manufacturing method of a body, Comprising: It has the process of forming a transparent metal layer, keeping the temperature of a transparent substrate at 65 degrees C or less.

Below, the typical example of the manufacturing method of the transparent conductor of this invention embodiment is demonstrated.
It is preferable that the manufacturing method of the transparent conductor of this embodiment is a manufacturing method of the aspect mainly including the process shown below. In addition, each component used for each process is explained in full detail later.

The transparent conductor manufactured by the method of manufacturing a transparent conductor according to the embodiment of the present invention includes a first high refractive index layer / first antisulfuration layer / transparent metal layer / second antisulfuration layer / second on a transparent substrate. It is set as the laminated body which laminates | stacks a high refractive index layer in order. The thickness of each layer is J. A. Woollam Co. Inc. It is measured with a VB-250 type VASE ellipsometer manufactured by the manufacturer. However, the average thickness of the underlayer is calculated from the formation speed of the manufacturer's nominal value of the sputtering apparatus.

(Step of forming the first high refractive index layer)
In this step, the first high refractive index layer is formed on the transparent substrate.
In this step, a sputtering method can be employed. In this case, for example, a dielectric such as a SPW-060 sputtering apparatus manufactured by Anelva Corporation has a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm. Sputtering is performed using an active material or an oxide semiconductor material. Note that the sputtering gas is not particularly limited, and may be, for example, argon (Ar), krypton (Kr), oxygen (O ₂ ), or the like.
Further, when the first high refractive index layer contains zinc sulfide (ZnS), this step contains a dielectric material or oxide semiconductor material having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm. And any one of the first high refractive index layer and the second high refractive index layer is a zinc sulfide-containing layer containing zinc sulfide (ZnS), and the first high refractive index layer and the second high refractive index layer are used. Is a step of forming.

Note that the method for forming the first high refractive index layer in this step is not particularly limited. In addition to the above-described sputtering method, general vapor deposition methods, ion plating methods, plasma CVD methods, thermal CVD methods, and the like can be used. A phase film formation method (also referred to as “deposition method”, “evaporation method”, or “synthesis method”) may be used. From the viewpoint of increasing the refractive index (density) of the first high refractive index layer 2, the first high refractive index layer 2 is a layer (film) formed by an electron beam evaporation method or a sputtering method. preferable. In the case of the electron beam evaporation method, it is desirable to have assistance such as IAD (ion assist) in order to increase the film density.

(Step of forming first sulfidation prevention layer)
In this step, a first antisulfurization layer is formed on the first high refractive index layer.
This step is a step of forming an anti-sulfurization layer containing at least one selected from metal oxides, metal fluorides, metal nitrides, and zinc (Zn) between the transparent metal layer and the zinc sulfide-containing layer. is there.
In this step, a sputtering method can be employed. In this case, for example, a sputtering apparatus such as SPW-060 sputtering apparatus manufactured by Anelva is used, and metal oxide, metal fluoride, metal nitride, and zinc (Zn) are used. At least one selected is sputtered. The sputtering gas is not particularly limited, and may be, for example, argon, krypton, oxygen, or the like.

In addition, the formation method of the 1st sulfurization prevention layer in this process is not specifically limited, In addition to the above-mentioned sputtering method, a general vapor phase such as a vacuum deposition method, an ion plating method, a plasma CVD method, and a thermal CVD method is used. A film forming method can be employed.

(Process of forming a transparent metal layer)
In this step, a transparent metal layer is formed on the first sulfurization prevention layer.
In this step, the transparent metal layer is formed while keeping the temperature of the transparent substrate at 65 ° C. or lower.
Note that the step of forming a layer adjacent to the transparent metal layer is preferably performed while keeping the temperature of the transparent substrate at 65 ° C. or lower. Thereby, it becomes easy to keep the temperature of the transparent substrate at 65 ° C. or lower when forming the transparent metal layer, and after forming the transparent metal layer, it is possible to suppress the movement of the particles constituting the transparent metal layer, As a result, the quality of the transparent metal layer can be further maintained.
Moreover, in this process, a sputtering method can be employed. In this case, for example, using an FTS Corporation facing target type sputtering apparatus, silver, copper, gold, platinum group, titanium, chromium, etc. have high conductivity. A transparent metal layer is formed by opposing sputtering of metal. The sputtering gas is not particularly limited, but a heavy rare gas such as krypton or xenon is preferable because a transparent metal layer with higher smoothness can be obtained and a transparent conductor with less light absorption can be obtained.
The forming gas pressure is preferably 1 Pa or less. When the gas pressure is high, the surface roughness Ra of the first high refractive index layer and the transparent metal layer is increased.

The surface roughness Ra means Ra = arithmetic average roughness (hereinafter also referred to as “surface roughness”), and is a value according to the surface roughness specified in JIS B601 (2001). The transparent metal layer according to the present invention preferably has a surface roughness Ra of 3 nm or less because a high-quality transparent metal layer (smooth transparent metal layer) can be secured. In the present invention, for measurement of Ra, a commercially available atomic force microscope (AFM) can be used. For example, it can be measured by the following method.

Using an AFM SPI3800N probe station and SPA400 multifunctional unit as the AFM, set the sample cut to a size of about 1 cm square on a horizontal sample stage on the piezo scanner, and place the cantilever on the sample surface. When the region where the atomic force works is reached, scanning is performed in the XY direction, and the unevenness of the sample at that time is captured by the displacement of the piezo in the Z direction. A piezo scanner that can scan XY 20 μm and Z 2 μm is used. The cantilever is a silicon cantilever SI-DF20 manufactured by Hitachi High-Tech Science Co., which has a resonance frequency of 120 to 150 kHz and a spring constant of 12 to 20 N / m, and is measured in a DFM mode (Dynamic Force Mode). A measurement area of 80 × 80 μm is measured at a scanning frequency of 1 Hz.

In addition, the formation method of the transparent metal layer in this process is not specifically limited, In addition to the above-described sputtering method, a general vapor deposition method such as a vacuum deposition method, an ion plating method, a plasma CVD method, and a thermal CVD method is used. The law can be adopted.

In the present invention, the formation speed at the time of forming the transparent metal layer is not particularly limited, but if it is 0.3 nm / s (3 Å / s) or more, light absorption (film absorption) by the transparent metal layer can be reduced. Therefore, it is preferable.
In addition, the formation speed at the time of forming a transparent metal layer uses a quartz-type film thickness meter etc. beforehand, calibrates the relationship between the formation time and the thickness of the formed transparent metal layer, and forms the transparent metal layer. It can be calculated by dividing the layer thickness by the formation time.

The method for adjusting the temperature of the transparent substrate is not particularly limited. For example, a thermo label (manufactured by NOF Corporation) is pasted on the transparent substrate, and the temperature under the conditions for forming each layer is confirmed and set in advance. Is mentioned.

(Step of forming the second sulfurization prevention layer)
In this step, the second sulfurization preventing layer is formed on the transparent metal layer.
This step is a step of forming an anti-sulfurization layer containing at least one selected from metal oxides, metal fluorides, metal nitrides, and zinc (Zn) between the transparent metal layer and the zinc sulfide-containing layer. is there.
In this step, a sputtering method can be employed. In this case, for example, a sputtering apparatus such as SPW-060 sputtering apparatus manufactured by Anelva is used, and metal oxide, metal fluoride, metal nitride, and zinc (Zn) are used. At least one selected is sputtered. In addition, although sputtering gas is not specifically limited, It is preferable not to contain oxygen gas.

The method for forming the second antisulfurization layer in this step is not particularly limited. In addition to the above-described sputtering method, a general gas deposition method such as a vacuum evaporation method, an ion plating method, a plasma CVD method, or a thermal CVD method can be used. Phase deposition method can be adopted, but prevention of sulfidation containing metal oxide, especially under vacuum and atmospheric conditions where oxygen gas is not introduced on the surface of the transparent metal layer opposite to the transparent substrate A formation method having a step of forming a layer is preferable. Thereby, it can suppress that oxygen plasma reacts with a transparent metal layer, the said transparent metal layer surface is roughened, and can reduce light absorption by extension. Note that the thickness of the second anti-sulfurization layer formed without introducing oxygen gas is preferably 5 nm or more when an oxide is further stacked on the second anti-sulfur layer. In the case where no object is laminated, the thickness is desirably 20 nm or less. Thereby, it can suppress more that oxygen plasma reacts with a transparent metal layer, and the said transparent metal layer surface becomes rough, and can further reduce light absorption further.
In addition, under the vacuum which concerns on this invention means the atmospheric pressure of 10 Pa or less.

(Step of forming the second high refractive index layer)
In this step, a second high refractive index layer is formed on the second sulfurization prevention layer.
In this step, a sputtering method can be employed. In this case, for example, a dielectric such as a SPW-060 sputtering apparatus manufactured by Anelva Corporation has a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm. Sputtering is performed using an active material or an oxide semiconductor material. In addition, although sputtering gas is not specifically limited, It is preferable not to contain oxygen gas.
In addition, when the second high refractive index layer contains zinc sulfide (ZnS), this step contains a dielectric material or an oxide semiconductor material having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm. And any one of the first high refractive index layer and the second high refractive index layer is a zinc sulfide-containing layer containing zinc sulfide (ZnS), and the first high refractive index layer and the second high refractive index layer are used. Is a step of forming.

Note that the method for forming the second high refractive index layer in this step is not particularly limited, and other than the above-described sputtering method, general vapor deposition methods, ion plating methods, plasma CVD methods, thermal CVD methods, and the like can be used. A phase film forming method may be used. From the viewpoint of increasing the refractive index (density) of the second high refractive index layer 4, the second high refractive index layer 4 is a layer (film) formed by an electron beam evaporation method or a sputtering method. preferable. From the viewpoint that the moisture permeability of the second high refractive index layer is lowered, the second high refractive index layer 4 is particularly preferably a film formed by a sputtering method.

An example of a manufacturing apparatus having the transparent conductor manufacturing method of the present invention will be described below with reference to FIGS.
As described above, the manufacturing apparatus for producing the transparent conductor of the present invention includes at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order. The transparent conductor is manufactured by the roll-to-roll method, and the method may be characterized by having a step of forming a transparent metal layer while keeping the temperature of the transparent substrate at 65 ° C. or less. The manufacturing apparatus 100 may not be used.

FIG. 4 is a schematic view showing an example of a manufacturing apparatus 100 having a manufacturing method for manufacturing the transparent conductor of the present invention. A manufacturing apparatus 100 shown in FIG. 4 is an apparatus that continuously manufactures the transparent conductor 10 using a roll-shaped transparent substrate 21.

The transparent substrate 21 unwound from the unwinding portion 101 placed in a reduced-pressure atmosphere enters the front chamber R1 through the guide rolls 102 and 103, and further passes through the slit roll 104 to perform surface treatment under a vacuum atmosphere. It is carried into the accumulation chamber R10 and the surface is subjected to dry cleaning and dehydration. The pressure in the surface treatment / accumulation chamber R10 is preferably set to 1 × 10 ⁻⁵ to 10 Pa.

Next, the transparent substrate 21 is continuously transferred from the surface treatment / accumulation chamber R10 to the formation chamber R20. A gate valve or a pressure adjusting chamber is provided between the surface treatment / accumulation chamber R10 and the formation chamber R20, and adjusts the differential pressure between the surface treatment / accumulation chamber R10 and the formation chamber R20.

In the manufacturing method of the present invention, first, any layer constituting the transparent conductor of the present invention is formed on the formation surface of the transparent substrate 21 being transferred in the forming chamber R20.

The forming chamber R20 includes a plurality of forming chambers R21 to R24, and an accumulator mechanism that absorbs the processing speed is provided between the forming chambers R21 to R24. The forming chambers R21 to R24 are evacuated independently and kept in a vacuum or a reduced pressure state, and the forming pressure varies depending on the forming method, and may be set to about 1 × 10 ⁻⁶ to 10 Pa. preferable.

The first formation chamber R21 performs a step of forming the first high refractive index layer.
That is, the first forming chamber R21 is formed on the transparent substrate 21 by the above-described forming method using a dielectric material or an oxide semiconductor material having a refractive index larger than that of the transparent substrate as a forming material for light having a wavelength of 570 nm. 1 A high refractive index layer is formed.
In the example of FIG. 4, in the first forming chamber R21, a dielectric material or oxide containing zinc sulfide (ZnS) as a forming material and having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm. The first high-refractive-index layer and the first high-refractive-index layer and the second high-refractive-index layer are made of a zinc sulfide-containing layer containing zinc sulfide (ZnS). 2 A step of forming a high refractive index layer is performed.
Here, the first formation chamber R21 will be described below with reference to FIG. FIG. 5 is a schematic configuration diagram in the first forming chamber R21.

The first forming chamber R21 includes a plurality of transport rollers 51 to 56 that transport the transparent substrate 21 along a predetermined transport path, a raw material supply unit 57 that faces the stacked surface of the transparent substrate 21 to be transported, and a stacked surface of the transparent substrate 21. The back surface cooling roller 58 etc. which are in contact with the opposite surface and cool the transparent substrate 21 and adjust the temperature of the transparent substrate 21 are provided inside.

Here, in the present invention, as shown in FIG. 6, the transparent substrate 21 has a plurality of first guide holes 211 opened at equal intervals in the conveyance direction (movement direction) at both ends in the width direction. Yes.
The transport rollers 51 to 56 have a plurality of protrusions projecting in the radial direction on the peripheral surface thereof. When the transparent substrate 21 is transported, the projection is inserted into the first guide hole 211 of the transparent substrate 21 so that the transparent substrate 21 is transported smoothly.

The raw material supply unit 57 has a formation mechanism corresponding to each method such as a vacuum deposition method, a sputtering method, or an ion plating method, and is provided to face the formation surface of the transparent substrate 21 to be conveyed. Thereby, formation of each layer can be performed with respect to a predetermined area | region among the formation surfaces of the transparent substrate 21 conveyed in the inside of 1st formation chamber R21.

The back surface cooling roller 58 is a roller member that is rotatably supported and includes a predetermined cooling mechanism. The back surface cooling roller 58 is provided on the opposite side of the raw material supply unit 57 with the transparent substrate 21 interposed therebetween, and comes into contact with the surface opposite to the formation surface of the transparent substrate 21, so that the raw material supply unit 57 of the transparent substrate 21 The region where the formation is performed is cooled, and the temperature of the transparent substrate 21 is adjusted.
The time and area where the rear cooling roller 58 and the transparent substrate 21 are in contact with each other are not particularly limited, but it is preferable that the temperature of the transparent substrate 21 be maintained at 65 ° C. or lower.

The transparent substrate 21 is stretched around the transport rollers 51 to 56, and the plurality of transport rollers 51 to 56 are rotationally driven to transport the transparent substrate 21 from the transport roller 51 toward the transport roller 52.

The inside of the first forming chamber R21 is configured as described above.

Subsequently, the formation chambers R22 to R24 will be described below with reference to FIG. 4 again. The second formation chamber R22 to the fourth formation chamber R24 have substantially the same configuration as the first formation chamber R21 described above, and the formation materials used are different.

The second forming chamber R22 is selected from a step of forming the first antisulfurization layer, that is, a metal oxide, a metal fluoride, a metal nitride, and zinc (Zn) between the transparent metal layer and the zinc sulfide-containing layer. The step of forming an antisulfurization layer containing at least one selected from the above is performed.
In the second forming chamber R22, the first sulfidation preventing layer is formed by the above-described forming method using at least one selected from the above-described metal oxide, metal fluoride, metal nitride, and zinc (Zn) as a forming material. .

3rd formation chamber R23 performs the process of forming a transparent metal layer, ie, the process of forming a transparent metal layer, keeping the temperature of a transparent substrate at 65 degrees C or less. In the third forming chamber R23, a transparent metal layer is formed by the above-described forming method using a conductive material such as metal or metal oxide as a forming material. In the case of the example of FIG. 4, this process is performed while the temperature of the transparent substrate 21 is kept at 65 ° C. or less by the rear cooling roller 58.

The fourth formation chamber R24 performs a step of forming the second high refractive index layer. In the fourth forming chamber R24, the second high-refractive-index layer is formed by the above-described forming method using a dielectric material or an oxide semiconductor material having a refractive index larger than that of the transparent substrate for light having a wavelength of 570 nm. The

Finally, the transparent substrate 21 in which the transparent substrate, the first high-refractive index layer, the first anti-sulfurization layer, the transparent metal layer, and the second high-refractive index layer are laminated on one surface is disposed in the winding chamber R60. And is wound up in the winding chamber R60.

In the manufacturing apparatus shown in FIG. 4, the transparent conductor has a transparent substrate, a first high refractive index layer, a first antisulfurization layer, a transparent metal layer, and a second high refractive index layer in this order. However, the present invention is not limited to this, and, for example, a configuration in which a plurality of first formation chambers R21 or fourth formation chambers R24 are provided and the third high refractive index layer may be formed.

Furthermore, the raw material supply part 57 of the fourth formation chamber R24 contains zinc sulfide (ZnS), and even in the fourth formation chamber R24, a dielectric material having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm or A first high refractive index layer containing an oxide semiconductor material and one of the first high refractive index layer and the second high refractive index layer being a zinc sulfide-containing layer containing zinc sulfide (ZnS) The step of forming the second high refractive index layer may be performed.
In this case, a second formation chamber R22 is further provided between the third formation chamber R23 and the fourth formation chamber R24 to form the second antisulfurization layer.

The forming chamber R20 has substantially the same configuration as the first forming chamber R21, in addition to the first forming chamber R21 to the fourth forming chamber R24 described above, and forms a base layer and a low refractive index layer, which will be described later, as the forming material. Depending on the material to be formed, a formation chamber for forming these layers may be provided as appropriate.

Next, each component used in the method for producing a transparent conductor of the present invention will be described in detail.

[Transparent substrate]
The transparent substrate 1 according to the present invention can be the same as the transparent substrate of various display devices. The transparent substrate 1 is a glass substrate, cellulose ester resin (for example, triacetylcellulose, diacetylcellulose, acetylpropionylcellulose, etc.), polycarbonate (PC) resin (for example, Panlite, Multilon (both manufactured by Teijin Limited)), cycloolefin Polymer (COP, such as ZEONOR (manufactured by ZEON CORPORATION), Arton (manufactured by JSR), APPEL (manufactured by Mitsui Chemicals)), acrylic resin (for example, polymethyl methacrylate, "acrylite (manufactured by Mitsubishi Rayon), Sumipex (Sumitomo) Chemical)), polyimide, phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyester resin (eg, polyethylene terephthalate (PET), polyethylene naphthalate), polyether sulfone, ABS / AS resin It can be a transparent resin film made of MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin), styrene block copolymer resin, etc. When the transparent substrate 1 is a transparent resin film, the film has 2 More than one resin may be included.

From the viewpoint of transparency, the transparent substrate 1 is made of glass film or cellulose ester resin, polycarbonate resin, polyester resin (especially polyethylene terephthalate), triacetyl cellulose, cycloolefin resin, phenol resin, epoxy resin, polyphenylene ether (PPE) resin, poly A film made of ether sulfone, ABS / AS resin, MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin) or styrene block copolymer resin is preferable.

The transparent substrate 1 is preferably highly transparent to visible light. Specifically, the average transmittance of light within the wavelength range of 400 to 800 nm (hereinafter also simply referred to as “transmittance”) is preferably 70% or more, more preferably 80% or more, More preferably, it is 85% or more. When the average light transmittance of the transparent substrate 1 is 70% or more, the light transmittance (transparency) of the transparent conductor 10 is likely to increase. The average absorption rate of light within the wavelength range of 400 to 800 nm of the transparent substrate 1 (hereinafter also simply referred to as “absorption rate”) is preferably 10% or less, more preferably 5% or less, even more preferably. Is 3% or less.

The average transmittance is measured by making light incident from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent substrate 1. On the other hand, the average absorptance can be calculated by making light incident from the same angle as the average transmittance and measuring the average reflectance (hereinafter also simply referred to as “reflectance”) of the transparent substrate 1. In the embodiment of the present invention, specifically, the average absorption rate (%) is calculated as (100− (average transmittance + average reflectance)). Average transmittance and average reflectance are measured with a spectrophotometer.

The refractive index of the transparent substrate 1 with respect to light having a wavelength of 570 nm is preferably in the range of 1.40 to 1.95, more preferably 1.45 to 1.75, even more preferably at a measurement temperature of 25 ° C. Is in the range of 1.45 to 1.70. The refractive index of the transparent substrate is usually determined by the material of the transparent substrate. The refractive index of the transparent substrate is measured with an ellipsometer.

The haze value of the transparent substrate 1 is preferably in the range of 0.01 to 2.5, more preferably in the range of 0.1 to 1.2. When the haze value of the transparent substrate is 2.5 or less, the haze value of the transparent conductor is suppressed. The haze value is measured with a haze meter.

The thickness of the transparent substrate 1 is preferably 1 μm to 20 mm, more preferably 10 μm to 2 mm. When the thickness of the transparent substrate 1 is 1 μm or more, the strength of the transparent substrate 1 is increased, and the first high refractive index layer 2 is hardly cracked or broken. On the other hand, if the thickness of the transparent substrate 1 is 20 mm or less, the flexibility of the transparent conductor 10 is sufficient. Furthermore, the thickness of the apparatus using the transparent conductor 10 can be reduced. Moreover, the apparatus using the transparent conductor 10 can also be reduced in weight.

Further, when the surface roughness Ra of the transparent substrate 1 is rough, the surface roughness is also transferred for each layer laminated thereon. That is, if the surface of the transparent substrate 1 is rough, a smooth transparent metal layer or the like cannot be formed.

[First high refractive index layer]
The first high-refractive index layer 2 according to the present invention is a layer for adjusting the light transmittance (optical admittance) of the conductive region a of the transparent conductor, that is, the region where the transparent metal layer 3 is formed. It is formed in the conduction region a of the body 10. The first high-refractive index layer 2 may be formed also in the insulating region b of the transparent conductor 10, but only the conductive region a is used from the viewpoint of making it difficult to visually recognize the pattern including the conductive region a and the insulating region b. It is preferable to be formed.

The first high refractive index layer 2 contains a dielectric material or an oxide semiconductor material having a refractive index higher than the refractive index of the transparent substrate 1 described above with respect to light having a wavelength of 570 nm. The refractive index of the dielectric material or oxide semiconductor material with respect to light with a wavelength of 570 nm is preferably 0.1 to 1.1 higher than the refractive index with respect to light with a wavelength of 570 nm of the transparent substrate 1, and is preferably 0.4 to 1.0. Larger is more preferable. On the other hand, the specific refractive index of the dielectric material or oxide semiconductor material included in the first high refractive index layer 2 with respect to light having a wavelength of 570 nm is preferably greater than 1.5 and is 1.7 to 2.5. More preferably, it is 1.8 to 2.5. When the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the optical admittance of the conductive region a of the transparent conductor 10 is sufficiently adjusted by the first high refractive index layer 2. The refractive index of the first high refractive index layer 2 is adjusted by the refractive index of the material included in the first high refractive index layer 2 and the density of the material included in the first high refractive index layer 2.

The dielectric material or oxide semiconductor material contained in the first high refractive index layer 2 may be an insulating material or a conductive material. The dielectric material or oxide semiconductor material can be a metal oxide. _TiO 2 _Examples of metal _{_{_{_{oxides, ITO, ZnO, Nb 2 O}}}} 5, ZrO 2, CeO 2, Ta 2 O 5, Ti 3 O 5, Ti 4 O 7, Ti 2 O 3, TiO, SnO 2, _{_{_{la 2 Ti 2 O 7, IZO}}} , IGZO (Indium gallium Zinc oxide), AZO (Aluminum doped Zinc oxide), GZO (gallium-doped Zinc oxide), ATO (Antimony Tin oxide), ICO, Bi 2 O 3, gallium oxide (Ga ₂ O ₃ ), GeO ₂ , WO ₃ , HfO ₂ , a-GIO and the like are included. The first high refractive index layer 2 may contain only one kind of the metal oxide or two or more kinds.

The dielectric material or oxide semiconductor material contained in the first high refractive index layer 2 can also be zinc sulfide (ZnS). When the first high refractive index layer 2 contains zinc sulfide, the first high refractive index layer is a zinc sulfide-containing layer according to the present invention.
When ZnS is contained in the first high refractive index layer 2, moisture hardly penetrates from the transparent substrate 1 side, and corrosion of the transparent metal layer 3 is suppressed. The first high refractive index layer 2 may contain only ZnS, and may contain other materials together with ZnS. The material contained together with ZnS is a metal oxide or silicon dioxide (SiO ₂ ), which can be the dielectric material or the oxide semiconductor material, and is particularly preferably SiO ₂ . When SiO ₂ is contained together with ZnS, the first high refractive index layer is likely to be amorphous, and the flexibility of the transparent conductor is likely to be enhanced.

When the first high refractive index layer 2 contains other materials together with ZnS, the amount of ZnS is 0.1 to 95% by mass with respect to the total number of moles of the materials constituting the first high refractive index layer 2. It is preferably 50 to 90% by mass, more preferably 60 to 85% by mass. When the ratio of zinc sulfide (ZnS) is high, the sputtering rate increases and the formation rate of the first high refractive index layer 2 increases. On the other hand, when many components other than ZnS are contained, the amorphous nature of the first high refractive index layer 2 is increased, and cracking of the first high refractive index layer 2 is suppressed.

The thickness of the first high refractive index layer 2 is preferably 15 to 150 nm, more preferably 20 to 80 nm. When the thickness of the first high refractive index layer 2 is 15 nm or more, the optical admittance of the conductive region a of the transparent conductor 10 is sufficiently adjusted by the first high refractive index layer 2. On the other hand, if the thickness of the first high refractive index layer 2 is 150 nm or less, the light transmittance of the region including the first high refractive index layer 2 is unlikely to decrease. The thickness of the first high refractive index layer 2 is measured with an ellipsometer.

Further, when the first high refractive index layer 2 is a layer patterned into a desired shape, the patterning method is not particularly limited. The first high refractive index layer 2 may be, for example, a layer formed in a pattern by a vapor deposition method by arranging a mask having a desired pattern on the surface to be formed; a known etching method It may be a layer patterned by.

[Second high refractive index layer]
The second high refractive index layer 4 according to the present invention is a layer for adjusting the light transmittance (optical admittance) of the conductive region a of the transparent conductor 10, that is, the region where the transparent metal layer 3 is formed, At least the conductive region a of the transparent conductor 10 is formed. The second high-refractive index layer 4 may be formed in the insulating region b of the transparent conductor 10, but is formed only in the conductive region a from the viewpoint of making it difficult to visually recognize the pattern formed of the conductive region a and the insulating region b. It is preferable that

The second high refractive index layer 4 includes a dielectric material or an oxide semiconductor material having a refractive index higher than that of the transparent substrate 1 described above. The refractive index of the dielectric material or oxide semiconductor material with respect to light with a wavelength of 570 nm is preferably 0.1 to 1.1 higher than the refractive index with respect to light with a wavelength of 570 nm of the transparent substrate 1, and is preferably 0.4 to 1.0. Larger is more preferable. On the other hand, the specific refractive index of the dielectric material or oxide semiconductor material included in the second high refractive index layer 4 with respect to light having a wavelength of 570 nm is preferably greater than 1.5 and is 1.7 to 2.5. More preferably, it is 1.8 to 2.5. When the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the optical admittance of the conductive region a of the transparent conductor 10 is sufficiently adjusted by the second high refractive index layer 4. The refractive index of the second high refractive index layer 4 is adjusted by the refractive index of the material included in the second high refractive index layer 4 and the density of the material included in the second high refractive index layer 4.

The dielectric material or oxide semiconductor material included in the second high refractive index layer 4 may be an insulating material or a conductive material. The dielectric material or oxide semiconductor material can be a metal oxide. The metal oxide may be the same as the metal oxide included in the first high refractive index layer. The second high refractive index layer 4 may contain only one kind of the metal oxide or two or more kinds.

The dielectric material or the oxide semiconductor material included in the second high refractive index layer 4 may be ZnS. When the second high refractive index layer 2 contains zinc sulfide, the second high refractive index layer is a zinc sulfide-containing layer according to the present invention.
When ZnS is contained in the second high refractive index layer 4, it is possible to suppress moisture from being transmitted from the second high refractive index layer 4 side and to prevent the transparent metal layer 3 from corroding. The second high refractive index layer 4 may contain only ZnS or may contain other materials together with ZnS. The material included together with ZnS is a metal oxide or SiO ₂ which can be the dielectric material or the oxide semiconductor material, particularly preferably SiO ₂ . When SiO ₂ is contained together with ZnS, the second high refractive index layer 4 is likely to be amorphous, and the flexibility of the transparent conductor 10 is likely to be enhanced.

When the second high refractive index layer 4 contains other materials together with ZnS, the amount of ZnS is 0.1 to 95 mass% with respect to the total number of moles of the components constituting the second high refractive index layer 4. It is preferably 50 to 90% by mass, more preferably 60 to 85% by mass. When the ratio of ZnS is high, the sputtering rate increases and the formation rate of the second high refractive index layer 4 increases. On the other hand, when the amount of components other than ZnS increases, the amorphousness of the second high refractive index layer 4 increases, and cracking of the second high refractive index layer 4 is suppressed.

The thickness of the second high refractive index layer 4 is 15 nm or more, and usually 150 nm or less. The thickness of the second high refractive index layer 4 is more preferably 15 to 150 nm, and further preferably 20 to 80 nm. When the thickness of the second high refractive index layer 4 is 15 nm or more, the optical admittance of the conductive region a of the transparent conductor 10 is sufficiently adjusted by the second high refractive index layer 4. On the other hand, if the thickness of the second high refractive index layer 4 is 150 nm or less, the light transmittance of the region including the second high refractive index layer 4 is unlikely to decrease. The thickness of the second high refractive index layer 4 is measured with an ellipsometer.

Further, when the second high refractive index layer 4 is a layer patterned into a desired shape, the patterning method is not particularly limited. The second high refractive index layer 4 may be, for example, a layer formed in a pattern by a vapor deposition method by arranging a mask having a desired pattern on the surface to be formed. Moreover, the layer patterned by the well-known etching method may be sufficient.

[Transparent metal layer]
The transparent metal layer 3 is a layer for conducting electricity in the transparent conductor 10. The transparent metal layer 3 may be formed on the entire surface of the transparent substrate 1 or may be patterned into a desired shape.

The metal contained in the transparent metal layer 3 is not particularly limited as long as it is a highly conductive metal, and may be, for example, silver, copper, gold, platinum group, titanium, chromium, or the like. The transparent metal layer 3 may contain only one kind of these metals or two or more kinds. From the viewpoint of high conductivity, the transparent metal layer is preferably made of silver or an alloy containing 90 at% or more of silver. The metal combined with silver can be zinc, gold, copper, palladium, aluminum, manganese, bismuth, neodymium, molybdenum, and the like. For example, when silver and zinc are combined, the sulfide resistance of the transparent metal layer is increased. When silver and gold are combined, salt resistance (NaCl) resistance increases. Furthermore, when silver and copper are combined, the oxidation resistance increases.

The plasmon absorption rate of the transparent metal layer 3 is preferably 10% or less (over the entire range) over a wavelength range of 400 to 800 nm, more preferably 7% or less, and even more preferably 5% or less. If there is a region having a large plasmon absorption rate in a part of the wavelength of 400 to 800 nm, the transmitted light of the conductive region a of the transparent conductor 10 is likely to be colored.

The plasmon absorption rate at a wavelength of 400 to 800 nm of the transparent metal layer 3 is measured by the following procedure.
(I) Platinum palladium is formed to 0.1 nm on a glass substrate by a magnetron sputtering apparatus. The average thickness of platinum palladium is calculated from the formation rate of the manufacturer's nominal value of the sputtering apparatus. After that, a 20 nm thick metal film is formed by sputtering on the substrate to which platinum palladium is attached.

(Ii) Then, measurement light is incident from an angle inclined by 5 ° with respect to the normal of the surface of the obtained metal film, and the transmittance and reflectance of the metal film are measured. Then, an absorptance (100− (transmittance + reflectance)) is calculated from the transmittance and reflectance at each wavelength, and this is used as reference data. The transmittance and reflectance are measured with a spectrophotometer.

(Iii) Subsequently, a transparent metal layer to be measured is formed on the same glass substrate. And about the said transparent metal layer, the transmittance | permeability and a reflectance are measured similarly. The reference data is subtracted from the obtained absorption rate, and the calculated value is defined as the plasmon absorption rate.

The thickness of the transparent metal layer 3 is 3 to 20 nm, preferably 5 to 9 nm, and more preferably 5 to 8 nm. In the transparent conductor 10 of the present invention, if the thickness of the transparent metal layer 3 is 10 nm or less, the metal inherent reflection hardly occurs in the transparent metal layer 3. Furthermore, when the thickness of the transparent metal layer 3 is 10 nm or less, the optical admittance of the transparent conductor 10 is easily adjusted by the first high refractive index layer 2 and the second high refractive index layer 4, and the surface of the conductive region a The reflection of light is easy to be suppressed. The thickness of the transparent metal layer 3 is measured with an ellipsometer.

The transparent metal layer 3 can be formed by any of the forming methods, but in order to change the average transmittance of the transparent metal layer, it is a film formed by sputtering or a film formed on an underlayer described later. Is preferred.

In the sputtering method, since the material collides with the object to be formed at a high speed at the time of formation, a dense and smooth film is easily obtained, so that the light transmittance of the transparent metal layer 3 is likely to be increased. Moreover, when the transparent metal layer 3 is a film formed by sputtering, the transparent metal layer 3 is hardly corroded even in an environment of high temperature and low humidity. The type of the sputtering method is not particularly limited, and may be an ion beam sputtering method, a magnetron sputtering method, a reactive sputtering method, a bipolar sputtering method, a bias sputtering method, a counter sputtering method, or the like. The transparent metal layer 3 is particularly preferably formed by a counter sputtering method. When the transparent metal layer 3 is formed by the facing sputtering method, the transparent metal layer 3 becomes dense and the surface smoothness is likely to increase. As a result, the surface electrical resistance of the transparent metal layer 3 becomes lower, and the light transmittance can be improved.

On the other hand, when the transparent metal layer 3 is formed on the underlayer, the underlayer becomes a growth nucleus when the transparent metal layer 3 is formed, so that the transparent metal layer 3 can be formed as a smooth layer. As a result, even if the transparent metal layer 3 is thin, plasmon absorption hardly occurs. In this case, the method for forming the transparent metal layer 3 is not particularly limited as described above, and a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, and a thermal CVD method is used. It can be.

Further, when the transparent metal layer 3 is a layer patterned into a desired shape, the patterning method is not particularly limited. The transparent metal layer 3 may be, for example, a layer formed by arranging a mask having a desired pattern; it may be a layer patterned by a known etching method.

[Sulfurization prevention layer]
In the embodiment of the present invention, the sulfidation prevention layer 5 will be described below assuming that the sulfidation prevention layer 5 includes the first sulfidation prevention layer 5a or the second sulfidation prevention layer 5b described above.

(First sulfurization prevention layer)
When the above-described first high refractive index layer 2 is a zinc sulfide-containing layer, as shown in FIG. 1, a first sulfurization prevention layer 5 a is provided between the first high refractive index layer 2 and the transparent metal layer 3. It is preferred that The first sulfidation preventing layer 5a may be formed also in the insulating region b of the transparent conductor 10, but from the viewpoint of making it difficult to visually recognize the pattern including the conductive region a and the insulating region b, the first sulfidation preventing layer 5a is formed only in the conductive region a. Preferably it is formed.

The first antisulfurization layer 5a is a layer containing at least one selected from metal oxide, metal fluoride, metal nitride, and zinc (Zn). Only one of these may be included in the first sulfurization prevention layer 5a, or two or more thereof may be included. However, when the first high refractive index layer 2, the first sulfidation preventing layer 5a, and the transparent metal layer 3 are continuously formed, the metal oxide can react with sulfur or adsorb sulfur. Preferably. When the metal oxide is a compound that reacts with sulfur, the reaction product of the metal oxide and sulfur preferably has high visible light permeability.

Examples of metal oxides include TiO ₂ , ITO, ZnO, Nb ₂ O ₅ , ZrO ₂ , CeO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , Ti ₄ O ₇ , Ti ₂ O ₃ , TiO, SnO _2. , La ₂ Ti ₂ O ₇ , IZO, IGZO, AZO, GZO, ATO, ICO, Bi ₂ O ₃ , a-GIO, Ga ₂ O ₃ , GeO ₂ , SiO ₂ , Al ₂ O ₃ , HfO ₂ , SiO, MgO, Y ₂ O ₃ and WO ₃ are included.
Examples of metal fluorides include LaF ₃ , BaF ₂ , Na ₅ Al ₃ F ₁₄ , Na ₃ AlF ₆ , AlF ₃ , MgF ₂ , CaF ₂ , BaF ₂ , CeF ₃ , NdF ₃ and YF _3. .
Examples of the metal nitride include Si ₃ N ₄ and AlN.

Here, the thickness of the first sulfidation preventing layer 5a is preferably a thickness capable of protecting the surface of the first high refractive index layer 2 from an impact when forming the transparent metal layer 3 described later. On the other hand, ZnS that can be contained in the first high refractive index layer has a high affinity with the metal contained in the transparent metal layer 3. Therefore, if the thickness of the first antisulfurization layer 5a is very thin and a part of the first high refractive index layer 2 is slightly exposed, a transparent metal layer grows around the exposed part, and the transparent metal Layer 3 tends to be dense. That is, the first antisulfurization layer 5a is preferably relatively thin, preferably 0.1 to 10 nm, more preferably 0.5 to 5 nm, and further preferably 1 to 3 nm. The thickness of the first sulfurization preventing layer 5a is measured with an ellipsometer.

When the first antisulfurization layer 5a is a layer patterned into a desired shape, the patterning method is not particularly limited. The first sulfidation preventing layer 5a may be a layer formed in a pattern by a vapor deposition method, for example, by placing a mask having a desired pattern on the surface to be formed, by a known etching method. It may be a patterned layer.

(Second antisulfurization layer 5b)
When the second high-refractive index layer is a zinc sulfide-containing layer, a second anti-sulfurization layer 5b may be provided between the transparent metal layer 3 and the second high-refractive index layer 4 as shown in FIG. preferable. The second sulfidation preventing layer 5b may be formed also in the insulating region b of the transparent conductor 10, but from the viewpoint of making it difficult to visually recognize the pattern composed of the conductive region a and the insulating region b, only the conductive region a. Preferably it is formed.

The second antisulfurization layer 5b is a layer containing at least one selected from metal oxide, metal fluoride, metal nitride, and zinc (Zn). Only one of these may be included in the second sulfurization prevention layer 5b, or two or more thereof may be included. The metal oxide, metal nitride, and metal fluoride may be the same as the metal oxide, metal nitride, and metal fluoride contained in the first high refractive index layer 2 described above.

On the other hand, the thickness of the second antisulfurization layer 5b is preferably a thickness capable of protecting the surface of the transparent metal layer 3 from an impact when the second high refractive index layer 4 is formed. On the other hand, the metal contained in the transparent metal layer 3 and the ZnS contained in the second high refractive index layer 4 have high affinity. Therefore, if the thickness of the second antisulfuration layer 5b is very thin and a part of the transparent metal layer 3 is slightly exposed, the transparent metal layer 3, the second antisulfurization layer 5b, and the second high refractive index layer. Adhesion with 4 tends to increase. Accordingly, the specific thickness of the second antisulfurization layer 5b is preferably 0.1 to 10 nm, more preferably 0.5 to 5 nm, and further preferably 1 to 3 nm. The thickness of the second sulfurization preventing layer 5b is measured with an ellipsometer.

The second antisulfurization layer 5b may be a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, or the like.

When the second antisulfurization layer 5b is a layer patterned into a desired shape, the patterning method is not particularly limited. The second antisulfurization layer 5b may be a layer formed in a pattern by a vapor deposition method, for example, by placing a mask having a desired pattern on the surface to be formed, and by a known etching method. It may be a patterned layer.

[Underlayer]
As described above, the transparent conductor 10 may include an underlayer that becomes a growth nucleus when the transparent metal layer 3 is formed. The underlayer is a layer formed on the substrate 1 side of the transparent metal layer 3 and adjacent to the transparent metal layer 3. That is, it may be a layer formed between the first high refractive index layer 2 and the transparent metal layer 3 or between the first antisulfurization layer 5 a and the transparent metal layer 3. The underlayer is preferably formed at least in the conductive region a of the transparent conductor, and may be formed in the insulating region b of the transparent conductor 10.

If the transparent conductor 10 includes a base layer, the smoothness of the surface of the transparent metal layer 3 is increased even if the transparent metal layer 3 is thin. The reason is as follows.

When the material of the transparent metal layer 3 is deposited, for example, on the first high refractive index layer 2 by a general vapor deposition method, atoms attached to the first high refractive index layer 2 are initially deposited at the initial stage of formation. It moves (move) and atoms gather together to form a lump (island structure). And a layer (film | membrane) grows clinging to this lump. Therefore, in the film at the initial stage of formation, there is a gap between the lumps, and the film is not conductive. When a lump further grows from this state, a part of the lump is connected and barely conducted. However, since there is still a gap between the lumps, plasmon absorption occurs. As the formation proceeds further, the lumps are completely connected and plasmon absorption is reduced. However, on the other hand, the original reflection of the metal occurs, and the light transmittance of the transparent metal layer decreases.

On the other hand, when a base layer made of a metal capable of suppressing migration is formed on the first high refractive index layer 2, the transparent metal layer 3 grows using the base layer as a growth nucleus. That is, the material of the transparent metal layer 3 can suppress migration, and the layer grows without forming the aforementioned island-like structure. As a result, a smooth transparent metal layer 3 can be obtained even if the thickness is small.

Here, the base layer may contain palladium, molybdenum, zinc, germanium, niobium, indium, alloys of these metals with other metals, oxides or sulfides of these metals (for example, ZnS). preferable. The underlayer may contain only one kind or two or more kinds.

The amount of palladium, molybdenum, zinc, germanium, niobium or indium contained in the underlayer is preferably 20% by mass or more, more preferably 40% by mass or more, and further preferably 60% by mass or more. When the metal is contained in the base layer in an amount of 20% by mass or more, the affinity between the base layer and the transparent metal layer 3 is increased, and the adhesion between the base layer and the transparent metal layer 3 is likely to be increased. It is particularly preferable that the underlayer contains palladium or molybdenum.

On the other hand, the metal that forms an alloy with palladium, molybdenum, zinc, germanium, niobium, or indium is not particularly limited, but may be a platinum group other than palladium, gold, cobalt, nickel, titanium, aluminum, chromium, and the like.

The thickness of the underlayer is 3 nm or less, preferably 0.5 nm or less, and more preferably a monoatomic film. The underlayer can also be a layer in which metal atoms are adhered to the transparent substrate 1 while being separated from each other. If the adhesion amount of the underlayer is 3 nm or less, the underlayer can be prevented from affecting the light transmittance and optical admittance of the transparent conductor 10. The presence or absence of the underlayer is confirmed by the ICP-MS method. Further, the thickness of the underlayer is calculated from the product of the formation speed and the formation time.

The formation method of the underlayer is not particularly limited, and may be a known method, for example, a sputtering method or a vapor deposition method can be applied. Examples of the sputtering method include an ion beam sputtering method, a magnetron sputtering method, a reactive sputtering method, a bipolar sputtering method, and a bias sputtering method. The sputtering time for forming the underlayer is appropriately selected according to the desired average thickness and formation rate of the underlayer. The formation rate by sputtering is preferably 0.01 to 1.5 nm / s (0.1 to 15 Å / s), more preferably 0.01 to 0.7 nm / s (0.1 to 7 Å / s). ).

On the other hand, examples of the vapor deposition method include a vacuum vapor deposition method, an electron beam vapor deposition method, an ion plating method, and an ion beam vapor deposition method. The deposition time is appropriately selected according to the desired thickness and formation rate of the underlayer. The deposition rate is preferably 0.01 to 1.5 nm / s (0.1 to 15 Å / s), more preferably 0.01 to 0.7 nm / s (0.1 to 7 Å / s). .

When the ground layer is a layer patterned into a desired shape, the patterning method is not particularly limited. The underlayer may be a layer formed in a pattern by a vapor deposition method, for example, by placing a mask having a desired pattern on the surface to be formed, or patterned by a known etching method. It may be a layer.

In addition, it is preferable that the surface roughness of the underlayer is approximately 3 nm or less in terms of Ra because a high-quality transparent metal layer (smooth transparent metal layer) can be formed.

[Low refractive index layer]
As described above, the transparent conductor 10 of the present invention has a low refractive index layer (not shown) for adjusting the light transmittance (optical admittance) of the conductive region a of the transparent conductor on the second high refractive index layer 4. May be provided. The low refractive index layer may be formed only in the conductive region a of the transparent conductor 10, or may be formed in both the conductive region a and the insulating region b of the transparent conductor 10.

The low refractive index layer has a refractive index with respect to light with a wavelength of 570 nm, which is higher than the refractive index with respect to light with a wavelength of 570 nm of the dielectric material or oxide semiconductor material included in the first high refractive index layer 2 and the second high refractive index layer 4. A dielectric material or oxide semiconductor material having a low rate is included. The refractive index with respect to light having a wavelength of 570 nm in the dielectric material or oxide semiconductor material contained in the low refractive index layer is the light of wavelength 570 nm of the material contained in the first high refractive index layer 2 and the second high refractive index layer 4. The refractive index is preferably 0.2 or more lower than the refractive index, more preferably 0.4 or more lower.

The specific refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the low refractive index layer is preferably less than 1.8, more preferably 1.30 to 1.6, Particularly preferred is 1.35 to 1.5. The refractive index of the low refractive index layer is mainly adjusted by the refractive index of the material included in the low refractive index layer and the density of the material included in the low refractive index layer.

The dielectric material or the oxide semiconductor material included in the low refractive index layer is MgF ₂ , SiO ₂ , AlF ₃ , CaF ₂ , CeF ₃ , CdF ₃ , LaF ₃ , LiF, NaF, NdF ₃ , YF ₃ , YbF _3. , Ga ₂ O ₃ , LaAlO ₃ , Na ₃ AlF ₆ , Al ₂ O ₃ , MgO and ThO ₂ . Dielectric material or oxide semiconductor materials among _{_{_{_{others, MgF 2, SiO 2, CaF}}}} 2, CeF 3, LaF 3, LiF, NaF, NdF 3, Na 3 AlF 6, Al 2 O 3, MgO, or is ThO ₂ In view of low refractive index, MgF ₂ and SiO ₂ are particularly preferable. Only one of these materials may be included in the low refractive index layer, or two or more of these materials may be included.

The thickness of the low refractive index layer is preferably 10 to 150 nm, more preferably 20 to 100 nm. When the thickness of the low refractive index layer is 10 nm or more, the optical admittance on the surface of the transparent conductor is easily finely adjusted. On the other hand, if the thickness of the low refractive index layer is 150 nm or less, the thickness of the transparent conductor is reduced. The thickness of the low refractive index layer is measured with an ellipsometer.

The low refractive index layer may be a layer formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method and a thermal CVD method. From the viewpoint of ease of formation and the like, the low refractive index layer is preferably a layer formed by electron beam evaporation or sputtering.

Further, when the low refractive index layer is a patterned layer, the patterning method is not particularly limited. The low refractive index layer may be, for example, a layer formed in a pattern by a vapor phase forming method by placing a mask having a desired pattern on the surface to be formed; patterned by a known etching method It may be a layer.

[Third high refractive index layer]
In the transparent conductor 10 of the present invention, a third high refractive index layer for adjusting the light transmittance (optical admittance) of the conductive region a of the transparent conductor may be further provided on the low refractive index layer. The third high refractive index layer may be formed only in the conductive region a of the transparent conductor 10, or may be formed in both the conductive region a and the insulating region b of the transparent conductor 10.

The third high refractive index layer preferably includes a dielectric material or an oxide semiconductor material having a refractive index higher than the refractive index of the transparent substrate 1 and the refractive index of the low refractive index layer.
The specific refractive index with respect to light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the third high refractive index layer is preferably larger than 1.5, more preferably 1.7 to 2.5. Preferably, it is 1.8 to 2.5. When the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the optical admittance of the conductive region a of the transparent conductor 10 is sufficiently adjusted by the third high refractive index layer. The refractive index of the third high refractive index layer is adjusted by the refractive index of the material included in the third high refractive index layer and the density of the material included in the third high refractive index layer.

The dielectric material or oxide semiconductor material contained in the third high refractive index layer may be an insulating material or a conductive material. The dielectric material or oxide semiconductor material is preferably a metal oxide or ZnS. Examples of the metal oxide include the metal oxide contained in the first high refractive index layer 2 or the second high refractive index layer 4 described above. The third high refractive index layer may contain only one kind of the metal oxide or ZnS, or may contain two or more kinds. A dielectric material such as SiO ₂ may be included together with the metal oxide and ZnS.

The thickness of the third high refractive index layer is not particularly limited, and is preferably 1 to 40 nm, and more preferably 5 to 20 nm. When the thickness of the third high refractive index layer is in the above range, the optical admittance of the conductive region a of the transparent conductor 10 is sufficiently adjusted. The thickness of the third high refractive index layer is measured with an ellipsometer.

The formation method of the third high refractive index layer is not particularly limited, and may be a layer formed by the same method as the first high refractive index layer 2 and the second high refractive index layer 4.

≪About optical admittance of transparent conductor≫
The reflectance R of the surface of the transparent conductor transmission region a (the surface of the transparent conductor opposite to the transparent substrate) is determined by the optical admittance Y _{env of the} medium on which light is incident and the surface of the transparent conductor transmission region a. determined from the equivalent admittance _{Y E.} Here, the medium on which the light is incident refers to a member or environment through which light incident on the transparent conductor passes immediately before the incident; a member or environment made of an organic resin. The relationship between the optical admittance Y _{env of the} medium on which light is incident and the equivalent admittance Y _E of the surface of the transparent conductor is expressed by the following equation.

Based on the above formula, the closer the value of | Y _env −Y _E | is to 0, the lower the reflectance R of the surface of the transparent conductor (transmission region a).

The optical admittance Y _{env of the} medium is obtained from the value (H / E) of the ratio between the electric field strength and the magnetic field strength, and is usually the same as the refractive index n _{env of the} medium. On the other hand, the equivalent admittance Y _E of the surface of the transparent region a of the transparent conductor is determined from the optical admittance Y of the layers constituting the transparent region a. For example, when the transparent conductor (transmission region a) consists of one layer, the equivalent admittance Y _E of the transparent conductor is equal to the of the layer optical admittance Y (refractive index).

On the other hand, when the transparent conductor (transmission region a) is composed of a laminate, the optical admittance Y _x (E _x H _x ) of the laminate from the first layer to the x-th layer is from the first layer to (x−1) It is represented by the product of the optical admittance Y _x-1 (E _x-1 H _x-1 ) of the laminate up to the layer and a specific matrix; specifically, the following formula (1) or formula (2) Is required.

・ When the x-th layer is a layer made of a dielectric material or an oxide semiconductor material

・ When the xth layer is an ideal metal layer

When the x-th layer is the outermost layer, the optical admittance Y _x (E _x H _x ) of the laminate from the transparent substrate to the outermost layer becomes the equivalent admittance Y _E of the transparent conductor.

In FIG. 7, for example, transparent substrate / first high refractive index layer (ZnS—SiO ₂ ) / first antisulfurization layer (ITO) / transparent metal layer (Ag) / second high refractive index layer (ZnS—SiO ₂ ) The admittance locus | trajectory of wavelength 570nm of the conduction | electrical_connection area | region a of a transparent conductor provided with was shown. The horizontal axis of the graph is the real part when the optical admittance Y of the region is represented by x + iy; that is, x in the equation, and the vertical axis is the imaginary part of the optical admittance; that is, y in the equation. In the transparent conductor of the above example, the first sulfidation preventing layer is sufficiently thin, and thus its optical admittance can be ignored.

7, the last coordinate in the admittance locus is equivalent admittance Y _E conductive region a. The distance between the coordinate (x _E , y _E ) of the equivalent admittance Y _E and the admittance coordinate Y _env (n _env , 0) (not shown) of the medium on which the light is incident is determined by the conduction region a of the transparent conductor. It is proportional to the surface reflectance R.

Here, in the transparent conductor of the present invention, the optical admittance at a wavelength of 570 nm of the surface of the transparent metal layer on the high refractive index layer side is Y1 (= x ₁ + ii ₁ ), and the wavelength of the surface on the intermediate layer side of the transparent metal layer is When the optical admittance at 570 nm is Y2 (= x ₂ + iy ₂ ), it is preferable that one or both of x ₁ and x ₂ is 1.6 or more. either one of x ₁ and x ₂ are, it tends enhanced light transmission of the transparent conductor If it is 1.6 or more. The reason will be described below.

The following relational expression is established between the admittance Y at the interface between the layers constituting the transparent conductor and the electric field strength E existing in each layer.

Based on the above relational expression, if the real part (x ₁ and x ₂ ) of the optical admittances Y1 and Y2 on the surface of the transparent metal layer is increased, the electric field strength E of the transparent metal layer is decreased and the electric field loss (light absorption) is reduced. Is suppressed. That is, the light transmittance of the transparent conductor is sufficiently increased.

Accordingly, either one or both of x ₁ and x ₂ is preferably 1.6 or more, more preferably 1.8 or more, and further preferably 2.0 or more. Any one of x ₁ and x ₂ may be 1.6 or more, but x ₁ is particularly preferably 1.6 or more. The _{x 1} and _{x 2} is preferably 7.0 or less, more preferably 5.5 or less. x ₁ is the refractive index of the first high refractive index layer and is adjusted by the thickness and the like of the first high refractive index layer. x ₂ is the refractive index of x ₁ values and transparent metal layer is adjusted by the thickness or the like of the first transparent metal layer. For example, if and refractive index of the first high refractive index layer is high, when the thickness of the first high refractive index layer is somewhat thicker, the value of x ₁ and x ₂ tends to increase. The absolute value (| x ₁ −x ₂ |) of the difference between x ₁ and x ₂ is preferably 1.5 or less, more preferably 1.0 or less, and even more preferably 0.8 or less. is there.

In addition, the admittance locus at a specific wavelength (570 nm in the present invention) is preferably line symmetric with respect to the horizontal axis of the graph. Admittance locus and is centered symmetrically on the horizontal axis of the graph, the coordinates of the equivalent admittance Y _E is at a wavelength other than the specific wavelength (e.g. 450nm or 700 nm), likely to be constant, at any wavelength, reflectance R becomes smaller. Therefore, a coordinate _{y 1} of the imaginary part of the Y1, the coordinate _{y 2} of the imaginary part of the Y2, it is preferable to satisfy the _{y 1} × _{y 2} ≦ 0. Furthermore, | y ₁ + y ₂ | is preferably less than 0.8, more preferably 0.5 or less, and still more preferably 0.3 or less.

Furthermore, it is preferable that the aforementioned y ₁ is sufficiently large. As described above, the value of the imaginary part of the optical admittance of the transparent metal layer is large, and the admittance locus greatly moves in the direction of the vertical axis (imaginary part). Therefore, if y ₁ is sufficiently large, the absolute value of the imaginary part of the admittance coordinates is likely to be within an appropriate range, and the admittance locus is likely to be line symmetric. y ₁ is preferably 0.2 or more, more preferably 0.3 to 1.5, and still more preferably 0.3 to 1.0. On the other hand, y ₂ described above is preferably −0.3 to −2.0, and more preferably −0.6 to −1.5.

On the other hand, the equivalent admittance coordinates (x _E , y _E ) of light having a wavelength of 570 nm in the conduction region a and the light of wavelength 570 nm of the member or environment (medium) in contact with the surface on the second high refractive index layer side of the transparent conductor. The distance from the equivalent admittance coordinate (n _env , 0) ((x _E −n _env ) ² + (y _E ) ² ) ^0.5 ) is preferably less than 0.5, more preferably 0.3. It is as follows. If the said distance is less than 0.5, the reflectance Ra of the surface of the conduction | electrical_connection area | region a will become small enough, and the light transmittance of the conduction | electrical_connection area | region a will increase.

Further, when the transparent metal layer 3 is patterned, an equivalent admittance coordinate (x _E , y _E ) of light with a wavelength of 570 nm in the conduction region a and an equivalent admittance coordinate (( x ( _b , y _b ))), ((x _E −x _b ) ² + (y _E −y _b ) ² ) ^0.5 ) is preferably less than 0.5, more preferably 0.3 or less. The coordinates of the equivalent admittance Y _E conductive region a, the coordinate of the equivalent admittance Y _b of the insulating region b is sufficiently close, so these patterns are hardly visually recognized. Furthermore, it is preferable that | (x _env −x _b ) ² + (Y _env −y _b ) ² − (x _env −x _E ) ² + (Y _env −yE) ² | If the said value is satisfy | filled, both the conduction | electrical_connection area | region a and the insulation area | region b will become difficult to visually recognize.

≪Physical properties of transparent conductor≫
The average transmittance of light having a wavelength of 400 to 800 nm of the transparent conductor of the present invention is preferably 83% or more, more preferably 85% or more, and still more preferably in both the conduction region a and the insulation region b. Is 88% or more. When the average transmittance in the above wavelength range is 83% or more, the transparent conductor can be applied to applications requiring high transparency to visible light.

On the other hand, the average transmittance of light having a wavelength of 400 to 1000 nm of the transparent conductor is preferably 80% or more in both the conduction region a and the insulation region b, more preferably 83% or more, and still more preferably 85%. That's it. When the average transmittance of light having a wavelength of 400 to 1000 nm is 80% or more, the transparent conductor is also applied to applications requiring transparency with respect to light in a wide wavelength range, such as a transparent conductive film for solar cells. can do.

On the other hand, the average absorptance of light having a wavelength of 400 to 800 nm of the transparent conductor is preferably 10% or less, more preferably 8% or less, and even more preferably in both the conduction region a and the insulation region b. 7% or less. In addition, the maximum value of the light absorptance of the transparent conductor having a wavelength of 400 to 800 nm is preferably 15% or less, more preferably 10% or less, both in the conduction region a and the insulation region b. Preferably it is 9% or less. On the other hand, the average reflectance of light having a wavelength of 500 to 700 nm of the transparent conductor is preferably 20% or less, more preferably 15% or less, and even more preferably in both the conduction region a and the insulation region b. Is 10% or less. The lower the average absorptance and average reflectance of the transparent conductor, the higher the aforementioned average transmittance.

The average transmittance and the average reflectance are preferably the transmittance and the reflectance under the usage environment of the transparent conductor. Specifically, when the transparent conductor is used by being bonded to an organic resin, it is preferable to measure the transmittance and the reflectance by disposing a layer made of the organic resin on the transparent conductor. On the other hand, when the transparent conductor is used in the air, it is preferable to measure the transmittance and reflectance in the air. The transmittance and the reflectance are measured with a spectrophotometer by allowing measurement light to enter from an angle inclined by 5 ° with respect to the normal of the surface of the transparent conductor. The absorptance is calculated from a calculation formula of 100− (transmittance + reflectance).

When the transparent conductor 10 includes the conduction region a and the insulation region b, it is preferable that the reflectance of the conduction region a and the reflectance of the insulation region b are approximated. Specifically, the difference ΔR between the luminous reflectance of the conduction region a and the luminous reflectance of the insulating region b is preferably 5% or less, more preferably 3% or less, and still more preferably It is 1% or less, particularly preferably 0.3% or less. On the other hand, the luminous reflectances of the conductive region a and the insulating region b are each preferably 5% or less, more preferably 3% or less, and further preferably 1% or less. The luminous reflectance is a Y value measured with a spectrophotometer (U4100; manufactured by Hitachi High-Technologies Corporation).

When the transparent conductor 10 includes the conduction region a and the insulation region b, the a ^* value and the b ^* value in the L ^* a ^* b ^* color system are preferably within ± 30 in any region. More preferably, it is within ± 5, more preferably within ± 3.0, and particularly preferably within ± 2.0. If the a ^* value and the b ^* value in the L ^* a ^* b ^* color system are within ± 30, both the conduction region a and the insulation region b are observed as colorless and transparent. The a ^* value and b ^* value in the L ^* a ^* b ^* color system are measured with a spectrophotometer.

The surface electric resistance of the conductive region a of the transparent conductor is preferably 50Ω / □ or less, more preferably 30Ω / □ or less. A transparent conductor having a surface electric resistance value of 50 Ω / □ or less in the conduction region can be applied to a transparent conductive panel for a capacitive touch panel. The surface electrical resistance value of the conduction region a is adjusted by the thickness of the transparent metal layer and the like. The surface electrical resistance value of the conduction region a is measured in accordance with, for example, JIS K7194, ASTM D257, or the like. It is also measured by a commercially available surface electrical resistivity meter.

≪Use of transparent conductor≫
The transparent conductors described above are used in various optoelectronic devices such as liquid crystal, plasma, organic electroluminescence, field emission, and other types of displays, as well as touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescence dimming elements. It can be preferably used for a substrate or the like.

At this time, the surface of the transparent conductor (for example, the surface opposite to the transparent substrate) may be bonded to another member via an adhesive layer or the like. In this case, as described above, it is preferable that the equivalent admittance coordinates of the surface of the transparent conductor and the admittance coordinates of the adhesive layer approximate each other. Thereby, reflection at the interface between the transparent conductor and the adhesive layer is suppressed.

On the other hand, when used in a configuration in which the surface of the transparent conductor is in contact with air, it is preferable that the admittance coordinates of the surface of the transparent conductor and the admittance coordinates of the air approximate each other. Thereby, reflection of light at the interface between the transparent conductor and air is suppressed.

Note that embodiments to which the present invention can be applied are not limited to the above-described embodiments, and can be appropriately changed without departing from the spirit of the present invention.

For example, for the purpose of preventing broadband reflection, a high refractive index material (with a refractive index of 1.8 or more for light having a wavelength of 570 nm) may be used for at least one of the upper and lower layers of the transparent metal layer. As a result, the visible light (450 to 700 nm) range can be kept substantially uniform and the transmittance can be maintained at 80% or more. However, the thickness of the transparent metal layer in this case is preferably 5 to 20 nm.
When the thickness of the transparent metal layer is 5 nm or more, it is possible to avoid a significant increase in plasmon absorption, and after forming an initial growth nucleus artificially, the transparent metal layer is formed at a low temperature. Even if it is formed, it becomes easy to obtain a sufficient transmittance. Further, when the thickness of the transparent metal layer is 20 nm or less, practical reflectance can be reduced, and it becomes easy to maintain a sufficient antireflection function.
Desirably, the refractive index for light having a wavelength of 570 nm is 1.8 or more, but by alternately combining a low refractive index and a high refractive index, the admittance (Y = x at the interface of one of the transparent metal layers). ₁ + iy ₁ , Y = x ₂ + iy ₂ ) may be adjusted so that x ₁ > 1.5 or x ₂ > 1.5.
You may adjust so that.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.
In this example, transparent conductors of Examples 1 to 18 and Comparative Example 1 were produced by a roll-to-roll method as shown in FIG. In the production of each transparent conductor, the laminated structure, the speed when forming the transparent metal layer, the temperature of the transparent substrate, and the formation method (evaporation method or sputtering method) are as shown in Table 1.
In addition, the temperature of the transparent substrate at the time of forming each layer was confirmed and adjusted in advance with a thermo label. Moreover, the formation speed when forming the transparent metal layer was calculated by calibrating the relationship between the formation time and the thickness of the transparent metal layer in advance.
Further, the refractive indexes shown below are all values at a temperature of 25 ° C.

[Example 1]
A transparent conductor of Example 1 was produced by laminating the following layers on a cycloolefin polymer (COP) (transparent substrate, refractive index with respect to light having a wavelength of 570 nm: 1.52).
Each layer was formed by keeping the temperature of the transparent substrate at 30 to 35 ° C.

(Formation of the first high refractive index layer)
A first high refractive index layer made of ZnS—SiO ₂ was formed to a thickness of 40 nm on one side of a COP having a thickness of 70 μm by resistance heating using a BMC-800T vapor deposition machine manufactured by SYNCHRON. The input current value at this time was 210 A, and the formation rate was 0.5 nm / s (5 Å / s).
The ratio (molar ratio) between ZnS and SiO ₂ was 80:20, and the refractive index of the first high refractive index layer with respect to light having a wavelength of 570 nm was 2.14.

(Formation of first antisulfurization layer)
On the first high refractive index layer, a first anti-sulfurization layer made of ZnO was formed to a thickness of 1 nm by resistance heating using a BMC-800T vapor deposition machine manufactured by SYNCHRON. The input current value at this time was 210 A, and the formation rate was 0.5 nm / s (5 Å / s).

(Formation of transparent metal layer)
On the first sulfidation prevention layer, a transparent metal layer made of Ag was formed to a thickness of 7 nm by resistance heating using a BMC-800T vapor deposition machine manufactured by SYNCHRON. The input current value at this time was 210 A, and the formation rate was 1.2 nm / s (12 Å / s).

(Formation of second sulfurization prevention layer)
On the transparent metal layer, a second anti-sulfurization layer made of ZnO was formed to a thickness of 1 nm by resistance heating using a BMC-800T vapor deposition machine manufactured by SYNCHRON. The input current value at this time was 210 A, and the formation rate was 0.5 nm / s (5 Å / s).

(Formation of second high refractive index layer)
On the second sulfurization preventive layer, a second high refractive index layer made of ZnS—SiO ₂ was formed to a thickness of 40 nm by resistance heating using a BMC-800T vapor deposition machine manufactured by SYNCHRON. The input current value at this time was 210 A, and the formation rate was 0.5 nm / s (5 Å / s). In addition, the refractive index with respect to the light of wavelength 570nm is the same value as a 1st high refractive index layer.

[Example 2 and Example 3]
The transparent conductors of Example 2 and Example 3 were produced in the same manner as the transparent conductor of Example 1, except that the temperature of the transparent substrate when forming each layer was as shown in Table 1. In addition, the refractive index with respect to the light of wavelength 570nm of a 1st high refractive index layer and a 2nd high refractive index layer is the same value as Example 1. FIG.

[Example 4]
Polyethylene terephthalate (PET, refractive index with respect to light having a wavelength of 570 nm was 1.64) was used as a transparent substrate, and the following layers were laminated on this PET to produce a transparent conductor of Example 4.
Each layer was formed on one side of PET having a thickness of 70 μm using SPW-060 manufactured by Anerva Co., Ltd. while maintaining the temperature of the transparent substrate at 35 to 40 ° C.

(Formation of the first high refractive index layer)
First, the vacuum chamber of the sputtering apparatus was evacuated to a high vacuum of 1 × 10 ⁻³ Pa. Thereafter, the sputtering pressure using Ar as a sputtering gas was 0.3 Pa, at room temperature, the target-side power 1.85 W / cm ^2, the formation rate of 0.2nm / s (2.0Å / s) the ZnS-SiO ₂ DC Sputtering was performed to form a first high refractive index layer with a thickness of 40 nm. The target-substrate distance was 86 mm. Note that the refractive index of the first high-refractive-index layer with respect to light having a wavelength of 570 nm is the same value as in Example 1.

(Formation of transparent metal layer)
Next, on the first high refractive index layer, Ar is used as the sputtering gas, the sputtering pressure is 0.5 Pa, the target side power is 1.85 W / cm ² , and the formation rate is 1.2 nm / s (12 Å / s) at room temperature. ) Ag was DC sputtered to form a transparent metal layer with a thickness of 7 nm. The target-substrate distance was 90 mm.

(Formation of second sulfurization prevention layer)
On the transparent metal layer, Ar is used as the sputtering gas and the sputtering pressure is 0.1 Pa. At room temperature, ZnO is formed at a target side power of 1.85 W / cm ² and a formation rate of 0.11 nm / s (1.1 Å / s). DC sputtering was performed to form a second antisulfurization layer with a thickness of 0.5 nm. The target-substrate distance was 90 mm.

(Formation of second high refractive index layer)
On the second sulfidation prevention layer, Ar is used as a sputtering gas, the sputtering pressure is 0.3 Pa, the target side power is 1.85 W / cm ² , and the formation rate is 0.2 nm / s (2.0 Å / s) at room temperature. ZnS—SiO ₂ was DC sputtered to form a second high refractive index layer with a thickness of 40 nm. The target-substrate distance was 86 mm. Note that the refractive index of the second high-refractive-index layer with respect to light having a wavelength of 570 nm is the same value as in Example 1.

[Example 5 and Example 6]
Transparent conductors of Examples 5 and 6 were produced in the same manner as in Example 4 except that the target-side power was adjusted so that the formation speed of the transparent metal layer was as shown in Table 2. In addition, the refractive index with respect to the light of wavelength 570nm of a 1st high refractive index layer and a 2nd high refractive index layer is the same value as Example 1. FIG.

[Example 7]
The first sulfidation prevention layer is not formed, and a glass film (transparent substrate with a refractive index of 1.52 for light having a wavelength of 570 nm) as a transparent substrate, ZnS—TiO ₂ as a first high refractive index layer and a second high refractive index layer. , Ag alloy (alloy containing 1.5 atomic% of Au and 0.5 atomic% of Cu in Ag) as the transparent metal layer, and IGZO as the second anti-sulfurization layer, forming the thickness and each layer A transparent conductor of Example 7 was produced in the same manner as in Example 1 except that the temperature of the transparent substrate was changed as shown in Table 1.
The ratio of ZnS and TiO ₂ in the ZnS-TiO ₂ (molar ratio), 80: a 20, the refractive index of the first high refractive index layer and the second high refractive index layer was 2.18.

[Example 8]
The second antisulfurizing layer is not formed, and the first antisulfurizing layer is formed as follows, and a cellulose triacetate having a thickness of 70 μm (TAC, refractive index with respect to light having a wavelength of 570 nm is 1.49) as a transparent substrate, ZnS—ZnO is used as the high refractive index layer, Ag alloy (alloy containing 1.5 atomic% of Au and 0.5 atomic% of Cu in Ag) is used as the transparent metal layer, and IGZO is used as the second high refractive index layer. A transparent conductor of Example 8 was produced in the same manner as in Example 4 except that the thickness of each layer and the temperature of the transparent substrate when forming each layer were as shown in Table 1.
The ratio (molar ratio) between ZnS and ZnO in ZnS—ZnO was 80:20, and the refractive index of the first high refractive index layer with respect to light having a wavelength of 570 nm was 2.16. The refractive index of the second high refractive index layer with respect to light having a wavelength of 570 nm was 2.09.

(Formation of first antisulfurization layer)
On the first high refractive index layer, Ar is used as the sputtering gas, the sputtering pressure is 0.1 Pa, the target side power is 1.85 W / cm ² , and the formation speed is 0.11 nm / s (1.1 Å / s) at room temperature. Then, ZnO was DC sputtered to form a first sulfidation preventing layer with a thickness of 1 nm on one side of the TAC. The target-substrate distance was 90 mm.

[Example 9]
Polycarbonate film having a thickness of 70 μm as a transparent substrate (PC, refractive index of 1.59 with respect to light having a wavelength of 570 nm), ZnS—Ga ₂ O ₃ as a first high refractive index layer, a first antisulfurization layer, and a second high refractive index A transparent conductor of Example 9 was produced in the same manner as Example 8 except that GZO was used as a layer and the thickness of each layer was as shown in Table 1.
The ratio of ZnS and _Ga 2 _{O 3} in the _ZnS-Ga 2 _{O 3} (molar ratio), 80: a 20, the refractive index for light of wavelength 570nm of the first high refractive index layer is 2.17 met It was. The refractive index of the second high refractive index layer with respect to light having a wavelength of 570 nm was 2.08.

[Example 10]
A transparent conductor of Example 10 was produced in the same manner as in Example 4 except that the sputtering gas for forming the transparent metal layer was krypton (Kr). In addition, the refractive index with respect to the light of wavelength 570nm of a 1st high refractive index layer and a 2nd high refractive index layer is the same value as Example 1. FIG.

[Example 11]
A transparent conductor of Example 11 was produced in the same manner as in Example 4 except that the target-side power was adjusted so that the formation speed when forming the transparent metal layer was 0.1 nm / s (1 Å / s). . In addition, the refractive index with respect to the light of wavelength 570nm of a 1st high refractive index layer and a 2nd high refractive index layer is the same value as Example 1. FIG.

[Example 12]
The second antisulfurization layer was formed under atmospheric conditions into which oxygen gas was introduced. Specifically, Ar and O ₂ (flow rate ratio: Ar: O ₂ = 10: 1) are used as the sputtering gas for forming the second sulfidation prevention layer, the sputtering pressure is set to 0.1 Pa, and the second sulfidation prevention is performed. A transparent conductor of Example 12 was produced in the same manner as Example 4 except that ITO was DC sputtered instead of ZnO to form a 10 nm thick layer. In addition, the refractive index with respect to the light of wavelength 570nm of a 1st high refractive index layer and a 2nd high refractive index layer is the same value as Example 1. FIG.

[Example 13]
A transparent conductor of Example 13 was produced in the same manner as the transparent conductor of Example 1, except that the temperature of the transparent substrate when forming each layer was as shown in Table 1. In addition, the refractive index with respect to the light of wavelength 570nm of a 1st high refractive index layer and a 2nd high refractive index layer is the same value as Example 1. FIG.

[Example 14]
A transparent conductor of Example 14 was produced in the same manner as Example 4 except that the target-side power was adjusted so that the formation speed of the transparent metal layer was as shown in Table 1. In addition, the refractive index with respect to the light of wavelength 570nm of a 1st high refractive index layer and a 2nd high refractive index layer is the same value as Example 1. FIG.

[Example 15]
A transparent conductor of Example 15 was produced in the same manner as in Example 4 except that PET was used as the transparent substrate and each layer was formed using an opposed target sputtering apparatus manufactured by FTS Corporation. In addition, the refractive index with respect to the light of wavelength 570nm of a 1st high refractive index layer and a 2nd high refractive index layer is the same value as Example 1. FIG.

[Example 16]
The first anti-sulfurization layer is not formed, and a transparent hard-coated polyethylene terephthalate film G1SBF manufactured by Kimoto Co., Ltd. (referred to as “PET / CHC” in Table 1. The refractive index for light having a wavelength of 570 nm is 1.59). 70 μm thick, ZnS as the first high refractive index layer and the second high refractive index layer, and GZO as the second antisulfurization layer, and the thickness of each layer and the temperature of the transparent substrate when forming each layer are shown in Table 1. A transparent conductor of Example 16 was produced in the same manner as in Example 1 except that the above was performed.
The refractive index of the first high refractive index layer and the second high refractive index layer was 2.34.

[Example 17]
The first anti-sulfurization layer is not formed, the above PET / CHC having a thickness of 70 μm is used as the transparent substrate, and GZO is used as the second anti-sulfur layer, and the thickness of each layer and the temperature of the transparent substrate when forming each layer are expressed. A transparent conductor of Example 17 was produced in the same manner as in Example 1 except that the procedure was as described in Example 1.
The refractive indexes of the first high refractive index layer and the second high refractive index layer are the same as those in Example 1.

[Example 18]
The first anti-sulfurization layer is formed as follows, the above PET / CHC having a thickness of 70 μm as a transparent substrate, ZnS as the first high-refractive index layer, GZO as the second anti-sulfur layer, and the second high-refractive index layer A transparent conductor of Example 18 was produced in the same manner as in Example 4 except that ITO was used and the thickness of each layer and the temperature of the transparent substrate when forming each layer were as shown in Table 1.
In addition, the refractive index with respect to the light of wavelength 570nm of a 2nd high refractive index layer was 2.10.

(Formation of first antisulfurization layer)
On the first high refractive index layer, Ar is used as the sputtering gas, the sputtering pressure is 0.1 Pa, the target side power is 1.85 W / cm ² , and the formation speed is 0.11 nm / s (1.1 Å / s) at room temperature. GZO was DC sputtered to form a first anti-sulfuration layer with a thickness of 1 nm. The target-substrate distance was 90 mm.

[Comparative Example 1]
A transparent conductor of Comparative Example 1 was produced in the same manner as in Example 1 except that the temperature of the transparent substrate when forming each layer was as shown in Table 1. In addition, the refractive index with respect to the light of wavelength 570nm of a 1st high refractive index layer and a 2nd high refractive index layer is the same value as Example 1. FIG.

(Measurement of light transmittance and light absorption)
About each produced said transparent conductor, the light transmittance and the light absorptivity were measured as follows.
Matching oil (refractive index = 1.52 manufactured by Nikon Corporation) was applied to the surface of the transparent conductor obtained in each example on the second high refractive index layer side. Then, a transparent conductor and a non-alkali glass substrate (EAGLE XG (thickness 7 mm × length 30 mm × width 30 mm) manufactured by Corning) were bonded together, and the transmittance and reflection of the transparent conductor from the alkali-free glass substrate side. At this time, the measurement light (for example, light having a wavelength of 400 to 800 nm) was incident on the conduction region from an angle inclined by 5 ° with respect to the normal of the surface of the alkali-free glass substrate, and Hitachi High Technologies The light transmittance and reflectance were measured with a spectrophotometer U4100, and the light absorptance was calculated from the calculation formula of 100− (transmittance + reflectance). Show.
The transmittance in Table 2 is the transmittance obtained by subtracting the surface reflectance lost at the air-alkali glass interface and the surface reflectance lost at the transparent conductor substrate-air interface (corresponding to the internal transmittance). .) Values are listed.

(Measurement of sheet resistance)
Using the resistivity meter (Loresta EP MCP-T360, manufactured by Mitsubishi Chemical Analytech Co., Ltd.), the sheet resistance value (Ω / □) was measured for each of the produced transparent conductors using the 4-terminal 4-probe method constant current application method. It was. The results are shown in Table 2.

(Summary)
As shown in Table 2, the transparent conductor of each example has a transmittance of 80% or more, a light absorption of 15% or less, and a sheet resistance value of 25Ω / □ or less. It is better than the transparent conductor.
In particular, Examples 1 to 10 and Examples 12 to 18 in which the formation rate of the transparent metal layer is 0.3 nm / s (3 Å / s) or more have a light absorption rate of 10% or less, a sheet resistance The value was 20Ω / □ or less, which was further improved as compared with Example 11.

8 and 9 show the relationship between the temperature or the formation speed of the transparent substrate and the light absorption rate.
FIG. 8 is a graph showing the relationship between the temperature of the transparent substrate and the light absorption rate when forming the transparent metal layer.
FIG. 9 is a graph showing the formation speed and the light absorption rate when forming the transparent metal layer.
From the above results, it was shown that the transparent conductor of the present invention can obtain a good light absorption rate.
Moreover, from the result of FIG. 8, in the method for producing a transparent conductor according to the present invention, if the transparent metal layer is formed while keeping the temperature of the transparent substrate at 65 ° C. or lower, the lower the temperature of the transparent substrate, the lower the temperature of the transparent substrate. It is assumed that the light absorption rate of the transparent conductor is improved.
Furthermore, from the result of FIG. 9, it is surmised that in the method for producing a transparent conductor of the present invention, the light absorption rate of the transparent conductor becomes better as the formation speed when forming the transparent metal layer is larger. The

As described above, the present invention is suitable for providing a method and a transparent conductor for manufacturing a low-resistance transparent conductor in which light absorption is reduced and reflection of light in the visible light region is prevented.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 1st high refractive index layer (zinc sulfide content layer)
3 Transparent metal layer 4 Second high refractive index layer (zinc sulfide-containing layer)
DESCRIPTION OF SYMBOLS 5 Antisulfation layer 5a 1st antisulfation layer 5b 2nd antisulfation layer 10 Transparent conductor

Claims

A transparent conductor manufacturing method for manufacturing a transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order by a roll-to-roll method,
A method for producing a transparent conductor, comprising the step of forming the transparent metal layer while maintaining the temperature of the transparent substrate at 65 ° C. or lower.
A dielectric material or an oxide semiconductor material having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm, and one of the first high refractive index layer and the second high refractive index layer 2. The method according to claim 1, further comprising forming the first high refractive index layer and the second high refractive index layer as a zinc sulfide-containing layer containing zinc sulfide (ZnS). A method for producing a transparent conductor.
The method further includes the step of forming an anti-sulfurization layer containing at least one selected from metal oxides, metal fluorides, metal nitrides, and zinc (Zn) between the transparent metal layer and the zinc sulfide-containing layer. The manufacturing method of the transparent conductor of Claim 2 characterized by the above-mentioned.
The step of forming the sulfidation preventive layer comprises the step of forming the sulfidation layer containing the metal oxide under a vacuum and an atmospheric condition in which oxygen gas is not introduced on the surface of the transparent metal layer opposite to the transparent substrate. The method for producing a transparent conductor according to claim 3, wherein the method is a step of forming a layer.
The transparent conductor according to any one of claims 1 to 4, wherein a formation speed when forming the transparent metal layer is 0.3 nm / s (3 Å / s) or more. Manufacturing method.
The method for producing a transparent conductor according to any one of claims 1 to 5, wherein krypton or xenon is used as a sputtering gas in the step of forming the transparent metal layer.
A transparent conductor manufactured by the method for manufacturing a transparent conductor according to any one of claims 1 to 6,
The first high refractive index layer and the second high refractive index layer contain a dielectric material or an oxide semiconductor material having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm, and One of the high refractive index layer and the second high refractive index layer is a zinc sulfide-containing layer containing zinc sulfide (ZnS), and
Between the transparent metal layer and the zinc sulfide-containing layer, an antisulfurization layer containing at least one selected from metal oxides, metal fluorides, metal nitrides, and zinc (Zn) is provided. Transparent conductor.
The transparent conductor according to claim 7, wherein the antisulfurization layer contains at least zinc oxide (ZnO) as the metal oxide.