WO2015068738A1

WO2015068738A1 - Transparent conductive body

Info

Publication number: WO2015068738A1
Application number: PCT/JP2014/079362
Authority: WO
Inventors: 一成多田; 仁一粕谷
Original assignee: コニカミノルタ株式会社
Priority date: 2013-11-05
Filing date: 2014-11-05
Publication date: 2015-05-14
Also published as: JPWO2015068738A1

Abstract

The invention of the present application addresses the problem of providing a transparent conductive body which is flexible, and which exhibits excellent optical transparency and reliability over an extended period of time. This transparent conductive body has, stacked therein in the given order: a transparent substrate; a first high refractive index layer including an oxide semiconductor material or a dielectric material having a refractive index with respect to light with a wavelength of 570 nm which is higher than that of the transparent substrate; a transparent metal film comprising an alloy of silver and a specific metal; and a second high refractive index layer including an oxide semiconductor material or a dielectric material having a refractive index with respect to light with wavelength of 570 nm which is higher than that of the transparent substrate. The first high refractive index layer and/or the second high refractive index layer is an amorphous layer which includes: ZnS; and a metal oxide or a metal fluoride.

Description

Transparent conductor

The present invention relates to a transparent conductor including a transparent metal film.

In recent years, transparent conductive films have been used for various devices such as electrode materials for display devices such as liquid crystal displays, plasma displays, inorganic and organic EL (electroluminescence) displays, electrode materials for inorganic and organic EL elements, touch panel materials, and solar cell materials. Has been.

As a material constituting such a transparent conductive film, metals such as Au, Ag, Pt, Cu, Rh, Pd, Al, and Cr, In ₂ O ₃ , CdO, CdIn ₂ O ₄ , Cd ₂ SnO ₄ , and TiO _{2 are used.} , SnO ₂ , ZnO, ITO (indium tin oxide) and other oxide semiconductors are known.

Here, in the touch panel type display device, 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.

Thus, it has been studied to use a vapor-deposited Ag film as a transparent conductive film (Patent Document 1). In order to increase the light transmittance of the transparent conductor, the Ag film is made of a film having a high refractive index (for example, niobium oxide (Nb ₂ O ₅ ), IZO (indium oxide / zinc oxide), ICO (indium cerium oxide), a- It has also been proposed that the film is sandwiched between GIO (a film made of gallium, indium, and oxygen) (Patent Documents 2 to 4, Non-Patent Document 1). Further, it has been proposed to sandwich an Ag film with a ZnS film, a ZnS—SiO ₂ film, and the like (

Non-patent Documents

2 and 3, and Patent Document 5).

Special table 2011-508400 gazette JP 2006-184849 A JP 2002-15623 A JP 2008-226581 A Chinese Patent Application No. 1026777012

However, as shown in Patent Documents 2 to 4 and Non-Patent Document 1, a transparent conductor in which an Ag film is sandwiched between niobium oxide, ITO, or the like has insufficient moisture resistance. As a result, when a transparent conductor is used in a humidity environment, there is a problem that the Ag film is easily corroded.

On the other hand, in the transparent conductor in which the Ag layer is sandwiched between the ZnS layer and the ZnS—SiO ₂ layer, Ag is sulfided and silver sulfide is easily generated. As a result, problems such as low light transmittance of the transparent conductor and high surface electrical resistance of the transparent conductor are likely to occur.

Furthermore, when the Ag layer is patterned, Ag ions eluted from the Ag layer may move and precipitate (migration). When such migration occurs, there is a problem that not only the light transmittance of the transparent conductor is lowered but also current leaks.

The present invention has been made in view of such a situation. An object of the present invention is to provide a flexible transparent conductor that has high light transmission and reliability over a long period of time.

That is, this invention relates to the following transparent conductors.
[1] A transparent substrate, a first high-refractive-index layer containing a dielectric material or an oxide semiconductor material having a refractive index of light having a wavelength of 570 nm higher than that of light of wavelength 570 nm of the transparent substrate, germanium, bismuth Silver, one or more metals selected from the group consisting of platinum group, copper, gold, molybdenum, zinc, gallium, tin, indium, neodymium, titanium, aluminum, tungsten, manganese, iron, nickel, yttrium, and magnesium A transparent metal film made of an alloy, and a second high-refractive-index layer containing a dielectric material or an oxide semiconductor material having a higher refractive index of light at a wavelength of 570 nm than the refractive index of light at a wavelength of 570 nm of the transparent substrate. A transparent conductor laminated in order, wherein at least one of the first high refractive index layer or the second high refractive index layer is made of ZnS and metal An amorphous layer containing a compound or a metal fluoride, a transparent conductor.
[2] The transparent conductor according to [1], wherein the metal oxide included in the amorphous layer is SiO ₂ .
[3] The transparent conductor according to [1] or [2], wherein the transparent metal film is a metal pattern patterned into a predetermined shape.

According to the present invention, it is possible to obtain a flexible transparent conductor that is less deteriorated over a long period of time and has a high light transmittance.

FIG. 1 is a schematic sectional view showing an example of a layer structure of a transparent conductor according to the present invention. FIG. 2 is a schematic sectional view showing another example of the layer structure of the transparent conductor of the present invention. FIG. 3 is a schematic diagram showing an example of a pattern composed of a conductive region and an insulating region of the transparent conductor of the present invention. 4A is a graph showing an admittance locus of the transparent conductor produced in Example 1 at a wavelength of 570 nm. FIG. 4B is a graph showing the spectral characteristics of the transparent conductor produced in Example 1. FIG. FIG. 5A is a graph showing an admittance locus at a wavelength of 570 nm of a transparent conductor having a transparent substrate / transparent metal film / high refractive index layer. FIG. 5B is a graph showing admittance trajectories of a transparent conductor / transparent metal film / high refractive index layer having a wavelength of 450 nm, a wavelength of 570 nm, and a wavelength of 700 nm. FIG. 6 is a graph showing the spectral characteristics of the transparent conductor produced in Example 2. FIG. 7 is a graph showing the spectral characteristics of the transparent conductor produced in Example 3. FIG. 8 is a graph showing the spectral characteristics of the transparent conductor produced in Example 4. FIG. 9 is a graph showing the spectral characteristics of the transparent conductor produced in Example 5. FIG. 10 is a graph showing the spectral characteristics of the transparent conductor produced in Example 6. FIG. 11 is a graph showing the spectral characteristics of the transparent conductor produced in Example 7. FIG. 12 is a graph showing the spectral characteristics of the transparent conductor produced in Example 8. FIG. 13 is a graph showing the spectral characteristics of the transparent conductor produced in Example 9. FIG. 14 is a graph showing the spectral characteristics of the transparent conductor produced in Example 10. FIG. 15 is a graph showing the spectral characteristics of the transparent conductor produced in Example 11. FIG. 16 is a graph showing the spectral characteristics of the transparent conductor produced in Example 12. FIG. 17 is a graph showing the spectral characteristics of the transparent conductor produced in Example 13. FIG. 18 is a graph showing the spectral characteristics of the transparent conductor produced in Example 14. FIG. 19 is a graph showing the spectral characteristics of the transparent conductor produced in Example 15. FIG. 20 is a graph showing the spectral characteristics of the transparent conductor produced in Example 16. FIG. 21 is a graph showing the spectral characteristics of the transparent conductor produced in Example 17. FIG. 22 is a graph showing the spectral characteristics of the transparent conductor produced in Example 18. FIG. 23 is a graph showing the spectral characteristics of the transparent conductor produced in Example 19. FIG. 24 is a graph showing the spectral characteristics of the transparent conductor produced in Example 20. FIG. 25 is a graph showing the spectral characteristics of the transparent conductor produced in Example 21. FIG. 26 is a graph showing the spectral characteristics of the transparent conductor produced in Example 22. FIG. 27 is a graph showing the spectral characteristics of the transparent conductor produced in Example 23. FIG. 28 is a graph showing the spectral characteristics of the transparent conductor produced in Example 24. FIG. 29 is a graph showing the spectral characteristics of the transparent conductor produced in Example 25. FIG. 30 is a graph showing the spectral characteristics of the transparent conductor produced in Example 26. FIG. 31 is a graph showing the spectral characteristics of the transparent conductor produced in Example 27. FIG. 32 is a graph showing the spectral characteristics of the transparent conductor produced in Example 28. FIG. 33 is a graph showing the spectral characteristics of the transparent conductor produced in Comparative Example 1. FIG. 34 is a graph showing the spectral characteristics of the transparent conductor produced in Comparative Example 3. FIG. 35 is a graph showing the spectral characteristics of the transparent conductor produced in Comparative Example 7. FIG. 36 is a graph showing the spectral characteristics of the transparent conductor produced in Example 33. FIG. 37 is a graph showing the spectral characteristics of the transparent conductor produced in Example 34.

Examples of the layer structure of the transparent conductor of the present invention are shown in FIGS. As shown in FIG. 1 and FIG. 2, the transparent conductor 100 of the present invention has a transparent substrate 1 / first high refractive index layer 2 / transparent metal film 3 / second high refractive index layer 4 laminated in this order. It consists of a laminate. In the transparent conductor 100 of the present invention, one or both of the first high refractive index layer 2 and the second high refractive index layer 4 are amorphous layers containing ZnS and a metal oxide or metal fluoride. Further, the transparent metal film 3 is made of an alloy of silver and another metal.

As described above, when the first high refractive index layer 2 or the second high refractive index layer 4 contains ZnS, the moisture resistance of the first high refractive index layer 2 and the second high refractive index layer 4 is likely to increase. In particular, when a metal oxide or a metal fluoride is contained together with ZnS, the crystallinity of the first high refractive index layer 2 and the second high refractive index layer 4 is lowered, and the first high refractive index layer 2 and the second high refractive index layer 2 and the second high refractive index layer 2 are reduced. The flexibility of the high refractive index layer 4 is likely to increase. However, when ZnS is contained in the first high-refractive index layer 2 or the second high-refractive index layer 4, there is a problem that the transparent metal film made of silver is easily sulfided and the light transmittance of the transparent conductor is likely to be lowered. there were.

On the other hand, in the transparent conductor of the present invention, although either or both of the first high refractive index layer 2 and the second high refractive index layer 4 contain ZnS, the transparent metal film 3 is made of silver and other metals. And alloy. Metals other than silver tend to localize on the surface of the transparent metal film 3. Then, an oxide film or the like is formed on the surface of the transparent metal film 3 by the metal. As a result, silver in the transparent metal film 3 is not easily sulfided, and a decrease in light transmittance of the transparent conductor is suppressed.

On the other hand, when the transparent metal film is composed only of silver, when the current is passed through the transparent conductor, the silver in the transparent metal film is ionized and is likely to move and precipitate (migration). And there also existed problems, such as an electric current leaking at the time of conduction | electrical_connection, or the light transmittance of a transparent conductor falling. On the other hand, when the transparent metal film 3 contains a metal other than silver, migration is suppressed. Therefore, a highly reliable transparent conductor can be obtained over a long period of time.

In the transparent conductor of the present invention, the transparent metal film 3 may be formed on the entire surface of the transparent substrate 1 as shown in FIG. 1, and is patterned into a desired shape as shown in FIG. May be. In the transparent conductor of the present invention, the region a where the transparent metal film 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 not including the transparent metal film 3 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 100. For example, when the transparent conductor 100 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 100 (laminated body) of the present invention may include layers other than the transparent substrate 1, the first high refractive index layer 2, the transparent metal film 3, and the second high refractive index layer 4. . For example, an underlayer (not shown) that becomes a growth nucleus when the transparent metal film 3 is formed may be included between the first high refractive index layer 2 and the transparent metal film 3; 4 may include a low refractive index layer (not shown) for adjusting the light transmittance of the transparent conductor 100. Furthermore, a third high refractive index layer (not shown) for adjusting the transparency of the transparent conductor may be included on the low refractive index layer. Further, an anti-sulfurization layer for preventing sulfidation of the transparent metal film 3 between the first high-refractive index layer 2 and the transparent metal film 3 or between the transparent metal film 3 and the second high-refractive index layer 4. (Not shown) may be included. However, the layers included in the transparent conductor 100 of 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 100 of the present invention. .

1. 1. Layer Configuration of Transparent Conductor 1-1) Transparent Substrate The transparent substrate 1 included in the transparent conductor 100 can be the same as the transparent substrate of various display devices. The transparent substrate 1 includes a glass substrate, a cellulose ester resin (for example, triacetylcellulose, diacetylcellulose, acetylpropionylcellulose, etc.), a polycarbonate resin (for example, Panlite, Multilon (both manufactured by Teijin Limited)), a cycloolefin resin (for example, ZEONOR (manufactured by Nippon Zeon), Arton (manufactured by JSR), APPEL (manufactured by Mitsui Chemicals)), acrylic resin (eg polymethyl methacrylate, acrylite (manufactured by Mitsubishi Rayon), Sumipex (manufactured by Sumitomo Chemical)) Polyimide, phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyester resin (for example, polyethylene terephthalate (PET), polyethylene naphthalate), polyethersulfone, ABS / AS resin, MBS resin, polystyrene Emissions, methacrylic resins, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resins), may be a transparent resin film comprising a styrene block copolymer resin. When the transparent substrate 1 is a transparent resin film, the film may contain two or more kinds of resins.

From the viewpoint of transparency, the transparent substrate 1 is a glass substrate, or a cellulose ester resin, a polycarbonate resin, a polyester resin (particularly polyethylene terephthalate), a triacetyl cellulose, a cycloolefin resin, a phenol resin, an epoxy resin, a polyphenylene ether (PPE) resin, A film made of polyethersulfone, 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 preferably has high transparency to visible light; the average transmittance of light having a wavelength of 450 to 800 nm is preferably 70% or more, more preferably 80% or more, and 85% or more. More preferably it is. When the average light transmittance of the transparent substrate 1 is 70% or more, the light transmittance of the transparent conductor 100 is likely to be increased. Further, the average absorptance of light having a wavelength of 450 to 800 nm of the transparent substrate 1 is preferably 10% or less, more preferably 5% or less, and further preferably 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 is calculated as average absorptance = 100− (average transmissivity + average reflectivity) by making light incident from the same angle as the average transmissivity and measuring the average reflectivity of the transparent substrate 1; . Average transmittance and average reflectance are measured with a spectrophotometer.

The refractive index of light having a wavelength of 570 nm of the transparent substrate 1 is preferably 1.40 to 1.95, more preferably 1.45 to 1.75, and still more preferably 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 0.01 to 2.5, more preferably 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. When the thickness of the transparent substrate is 1 μm or more, the strength of the transparent substrate 1 is increased, and it is difficult to crack or tear the first high refractive index layer 2 during production. On the other hand, when the thickness of the transparent substrate 1 is 20 mm or less, the flexibility of the transparent conductor 100 is sufficient. Furthermore, the thickness of the apparatus using the transparent conductor 100 can be reduced. Moreover, the apparatus using the transparent conductor 100 can also be reduced in weight.

When particularly high flexibility is required for the transparent conductor, the thickness of the transparent substrate 1 is preferably 1 μm to 20 mm, more preferably 1 μm to 500 μm. When the thickness of the transparent substrate 1 is 20 mm or less, the flexibility of the transparent substrate 1 is likely to increase.

1-2) First High Refractive Index Layer The first high refractive index layer 2 adjusts the light transmittance (optical admittance) of the conductive region a of the transparent conductor, that is, the region where the transparent metal film 3 is formed. Is a layer. Accordingly, the first high refractive index layer 2 is formed in the conductive region a of the transparent conductor. Although the first high refractive index layer 2 may be formed also in the insulating region b of the transparent conductor 100, as will be described later, from the viewpoint of making it difficult to visually recognize the pattern composed of the conductive region a and the insulating region b. It is preferable that it is formed only in the conduction region a.

The first high refractive index layer 2 includes a dielectric material or an oxide semiconductor material having a refractive index higher than the refractive index of the transparent substrate 1 described above. The refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material is preferably 0.1 to 1.1 larger than the refractive index of light having 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 light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the first high refractive index layer 2 is preferably larger 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 100 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 the oxide semiconductor material may be a metal oxide having the above refractive index. Examples of the metal oxide having the refractive index include TiO ₂ , ITO (indium tin oxide), ZnO, Nb ₂ O ₅ , ZrO ₂ , CeO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , and Ti ₄ O _7. , Ti ₂ O ₃ , TiO, SnO ₂ , La ₂ Ti ₂ O ₇ , IZO (indium oxide / zinc oxide), AZO (Al-doped ZnO), GZO (Ga-doped ZnO), ATO (Sb-doped SnO), ICO ( Indium cerium oxide), IGZO (indium / gallium / zinc oxide), SGZO (tin / gallium / zinc oxide), TIZO (indium / zinc, tin oxide), Bi ₂ O ₃ , Ga ₂ O ₃ , GeO ₂ , WO ₃ , HfO ₂ , In ₂ O ₃ , a-GIO (amorphous oxide composed of gallium, indium and oxygen), etc. It is. The first high refractive index layer 2 may be a layer containing only one kind of the metal oxide or a layer containing two or more kinds.

In addition, the dielectric material or the oxide semiconductor material included in the first high refractive index layer 2 may be ZnS. When ZnS is contained in the first high refractive index layer 2, it becomes difficult for moisture to permeate from the transparent substrate 1 side, and corrosion of the transparent metal film 3 is suppressed. Moreover, since ZnS and silver have high affinity, even if silver is thin, it is easy to form a continuous film. However, ZnS has a relatively high crystallinity, and a film made of only ZnS tends to be a rigid film. Therefore, the first high refractive index layer 2 is preferably an amorphous layer containing ZnS and a metal oxide or metal fluoride. The metal oxide or metal fluoride contained in the amorphous layer is not particularly limited as long as it is a compound capable of amorphizing ZnS, and SiO ₂ , Na ₅ Al ₃ F ₁₄ , Na ₃ AlF ₆ , AlF ₃ , _{_{_{_{MgF 2, CaF 2, BaF 2}}}} , Al 2 O 3, YF 3, LaF 3, CeF 3, NdF 3, ZrO 2, SiO, MgO, Y 2 O 3, ZnO, In 2 O 3, Ga 2 O 3 , etc. It can be. Only one of these may be included in the first high refractive index layer 2, or two or more thereof may be included. These compounds are particularly preferably SiO _2.

When the first high refractive index layer 2 is an amorphous layer, the amorphous layer preferably contains 0.1 to 95% by volume of ZnS, more preferably 50 to 90% by volume with respect to the total volume of the amorphous layer. %, And more preferably 70 to 85% by volume. When the ratio of ZnS is high, the sputtering rate increases and the film formation rate of the first high refractive index layer 2 increases. On the other hand, when a large amount of metal oxide is contained, the amorphousness of the first high refractive index layer 2 increases, 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 100 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. Moreover, if the thickness of the 1st high refractive index layer 2 is 150 nm or less, the flexibility of the 1st high refractive index layer 2 will increase easily, and the flexibility of a transparent conductor can also be improved. The thickness of the first high refractive index layer 2 is measured with an ellipsometer.

The first high refractive index layer 2 can 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. 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 preferably a layer formed by an electron beam evaporation method or a sputtering method. 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.

Here, when the first high refractive index layer 2 is an amorphous layer containing ZnS and a metal oxide, a mixture obtained by mixing ZnS and a metal oxide in a desired ratio may be used as a vapor deposition source or a sputtering target. Further, ZnS and metal oxide may be co-evaporated or co-sputtered.

Further, when the first high refractive index layer 2 is a layer patterned in 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 film formation surface; It may be a layer patterned by an etching method.

1-3) Transparent Metal Film The transparent metal film 3 of the present invention is a film for conducting electricity in the transparent conductor 100. The transparent metal film 3 may be formed on the entire surface of the transparent substrate 1 as described above, or may be patterned into a desired shape.

The transparent metal film 3 is made of an alloy of silver and a metal other than silver. When the metal other than silver contained in the transparent metal film 3 together with silver is an alloy with silver, the metal tends to localize on the surface of the transparent metal film 3 or the bonding strength between silver and sulfur. A metal having a strong bonding force is preferred. Specifically, metals other than silver contained in the transparent metal film 3 together with silver are germanium, bismuth, platinum group, copper, gold, molybdenum, zinc, gallium, tin, indium, neodymium, titanium, aluminum, tungsten, manganese, Iron, nickel, yttrium, and magnesium. Germanium, bismuth, palladium, copper, gold, and neodymium are preferable. The transparent metal film 3 may contain only one kind of these metals or two or more kinds.

The amount of metal other than silver contained in the transparent metal film 3 is preferably 0.01 to 10 at%, more preferably 0.1 to 5 at% with respect to the total amount of atoms constituting the transparent metal film 3. %, And more preferably 0.2 to 3 at%. If the transparent metal film 3 contains other metals at 0.1 at% or more, silver sulfidation is easily suppressed. On the other hand, if the amount of the other metal contained in the transparent metal film 3 is 10 at% or less, the light transmittance of the transparent metal film 3 is likely to increase. The kind and content of each atom contained in the transparent metal film are specified by, for example, the XPS method.

The plasmon absorption rate of the transparent metal film 3 is preferably 10% or less (over the entire range) over a wavelength range of 400 nm to 800 nm, more preferably 7% or less, and further preferably 5% or less. If there is a region having a large plasmon absorption rate in a part of the wavelength of 400 nm to 800 nm, the transmitted light of the conductive region a of the transparent conductor 100 is likely to be colored.

The plasmon absorption rate at a wavelength of 400 nm to 800 nm of the transparent metal film 3 is measured by the following procedure.
(I) A platinum palladium film is formed to a thickness of 0.1 nm on a glass substrate using a magnetron sputtering apparatus. The average thickness of platinum palladium is calculated from the film forming speed and the like of the manufacturer's nominal value of the sputtering apparatus. Thereafter, a film made of metal is formed to a thickness of 20 nm on the substrate to which platinum palladium is adhered by sputtering.

(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 the reflectance of the metal film are measured. Then, from the transmittance and reflectance at each wavelength, absorption rate = 100− (transmittance + reflectance) is calculated and used as reference data. The transmittance and reflectance are measured with a spectrophotometer.

(Iii) Subsequently, the transmittance and reflectance of the transparent metal film to be measured are measured in the same manner. Then, 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 film 3 is preferably 10 nm or less, preferably 3 to 9 nm, and more preferably 5 to 8 nm. If the transparent metal film 3 has a thickness of 10 nm or less, the transparent metal film 3 is less likely to reflect the original metal. Furthermore, when the thickness of the transparent metal film 3 is 10 nm or less, the optical admittance of the transparent conductor 100 is easily adjusted by the first high refractive index layer 2 and the second high refractive index layer 4 as described later, and the conduction Reflection of light on the surface of the region a is likely to be suppressed. The thickness of the transparent metal film 3 is measured with an ellipsometer.

The transparent metal film 3 can be a film formed by any film forming method, but as described above, in order to make the average transmittance of light with a wavelength of 400 to 1000 nm of the transparent conductor 80% or more. A film formed by a sputtering method; a film formed by an ion assist method or the like; or a film formed on an underlayer described later.

In the sputtering method or the ion assist method, since the material collides with the deposition target at high speed during film formation, it is easy to obtain a dense and smooth film; the light transmittance of the transparent metal film 3 is likely to increase. 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 film 3 is particularly preferably a film formed by a counter sputtering method. When the transparent metal film 3 is a film formed by the facing sputtering method, the transparent metal film 3 becomes dense and the surface smoothness is likely to increase. As a result, the surface electrical resistance of the transparent metal film 3 becomes lower and the light transmittance is likely to increase.

When the transparent metal film 3 is formed by sputtering, an alloy in which silver and other metals are mixed in a desired ratio may be used as a sputtering target, and silver and other metals may be used as sputtering targets.

On the other hand, when the transparent metal film 3 is a film formed on an underlayer described later, the underlayer becomes a growth nucleus when the transparent metal film 3 is formed, so that the transparent metal film 3 tends to be a smooth film. . As a result, even if the transparent metal film 3 is thin, plasmon absorption hardly occurs. In this case, the method for forming the transparent metal film 3 is not particularly limited, and may be 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.

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

1-4) Second High Refractive Index Layer The second high refractive index layer 4 adjusts the light transmittance (optical admittance) of the conductive region a of the transparent conductor 100, that is, the region where the transparent metal film 3 is formed. And is a layer for protecting the transparent metal film 3 from external moisture and the like. Therefore, the second high refractive index layer 4 is formed in the conduction region a of the transparent conductor 100. The second high-refractive index layer 4 may be formed in the insulating region b of the transparent conductor 100. However, as will be described later, the second high-refractive index layer 4 is conductive from the viewpoint of making it difficult to visually recognize the pattern including the conductive region a and the insulating region b. It is preferably formed only in the region a.

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 light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material is preferably 0.1 to 1.1 larger than the refractive index of light having 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 light with a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the second high refractive index layer 4 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 100 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 contained in the second high refractive index layer 4 may be an insulating material or a conductive material. The dielectric material or the oxide semiconductor material may be a metal oxide having the above refractive index. The metal oxide can be the same as the metal oxide contained in the first high refractive index layer. The second high refractive index layer 4 may be a layer containing only one kind of the metal oxide or a layer containing 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 ZnS is contained in the second high refractive index layer 4, it becomes difficult for moisture to permeate from the second high refractive index layer 4 side, and corrosion of the transparent metal film 3 is suppressed. However, ZnS has a relatively high crystallinity, and a film made of only ZnS tends to be a rigid film. Therefore, the second high refractive index layer 4 is preferably an amorphous layer containing ZnS and a metal oxide or metal fluoride. The metal oxide or metal fluoride contained in the amorphous layer is not particularly limited as long as it is a compound capable of amorphizing ZnS, and the metal oxide or metal fluoride contained in the first high refractive index layer 2 together with ZnS. It can be the same compound as the compound. These may be included in the second high refractive index layer 4 alone or in combination of two or more. Compounds included with ZnS is particularly preferably SiO _2.

When the second high refractive index layer 4 is an amorphous layer, the amorphous layer preferably contains 0.1 to 95% by volume of ZnS, more preferably 50 to 90% by volume with respect to the total volume of the amorphous layer. %, And more preferably 70 to 85% by volume. When the ratio of ZnS is high, the sputtering rate is increased, and the deposition rate of the second high refractive index layer 4 is increased. On the other hand, when many components other than ZnS are contained, the amorphous nature 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 preferably 15 nm or more and 150 nm or less. The thickness of the second high refractive index layer 4 is more preferably 15 to 150 nm, still more 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 100 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. Furthermore, the flexibility of the second high refractive index layer 4 is likely to increase. The thickness of the second high refractive index layer 4 is measured with an ellipsometer.

The film formation method of the second high refractive index layer 4 is not particularly limited, and is 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. Layer. From the viewpoint that the moisture permeability of the second high refractive index layer 4 is lowered, the second high refractive index layer 4 is particularly preferably a film formed by sputtering.

Here, when the second high refractive index layer 4 is an amorphous layer containing ZnS and a metal oxide, a mixture obtained by mixing ZnS and a metal oxide in a desired ratio may be used as a vapor deposition source or a sputtering target. Further, ZnS and metal oxide may be co-evaporated or co-sputtered.

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 placing a mask having a desired pattern on the deposition surface. Moreover, the layer patterned by the well-known etching method may be sufficient.

1-5) Underlayer As described above, an underlayer serving as a growth nucleus when the transparent metal film 3 is formed may be included between the first high refractive index layer 2 and the transparent metal film 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 100.

As described above, when the transparent conductor 100 includes an underlayer, the smoothness of the surface of the transparent metal film 3 is enhanced even if the transparent metal film 3 is thin. The reason is as follows.

When the material of the transparent metal film 3 is deposited on the first high refractive index layer 2 by a general vapor deposition method, atoms attached on the first high refractive index layer 2 are migrated at the initial stage of film formation. (Move) and atoms gather together to form a lump (island structure). And a film grows clinging to this lump. Therefore, in the film at the initial stage of film formation, there is a gap between the lumps and it 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 film formation proceeds further, the lumps are completely connected and plasmon absorption is reduced. However, on the other hand, the intrinsic reflection of the metal occurs, and the light transmittance of the film decreases.

On the other hand, when a base layer made of a metal that is difficult to migrate is formed on the first high refractive index layer 2, the transparent metal film 3 grows using the base layer as a growth nucleus. That is, the material of the transparent metal film 3 is difficult to migrate, and the film grows without forming the island-like structure described above. As a result, it becomes easy to obtain a smooth transparent metal film 3 even if the thickness is small.

Here, the base layer contains palladium, molybdenum, zinc, germanium, niobium, or indium; or an alloy of these metals with other metals, or an oxide or sulfide of these metals (for example, ZnS). Is preferred. 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 film 3 is increased, and the adhesion between the base layer and the transparent metal film 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, or 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 film in which metal atoms adhere to the transparent substrate 1 with a distance therebetween. If the adhesion amount of the underlayer is 3 nm or less, the underlayer is unlikely to affect the optical admittance of the transparent conductor 100. 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 film formation speed and the film formation time.

The underlayer can be a layer formed by sputtering or vapor deposition. 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 during the underlayer film formation is appropriately selected according to the desired average thickness of the underlayer and the film formation speed. The sputter deposition rate is preferably from 0.1 to 15 Å / second, more preferably from 0.1 to 7 秒 / second.

On the other hand, examples of the vapor deposition method include vacuum vapor deposition method, electron beam vapor deposition method, ion plating method, ion beam vapor deposition method and the like. The deposition time is appropriately selected according to the desired thickness of the underlayer and the film formation rate. The deposition rate is preferably 0.1 to 15 Å / second, more preferably 0.1 to 7 Å / second.

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

1-6) Low Refractive Index Layer As described above, in the transparent conductor 100 of the present invention, the light transmittance (optical admittance) of the conductive region a of the transparent conductor is adjusted on the second high refractive index layer 4. A low refractive index layer may be included. The low refractive index layer may be formed only in the conductive region a of the transparent conductor 100, or may be formed in both the conductive region a and the insulating region b of the transparent conductor 100.

The low refractive index layer includes a dielectric material or an oxide semiconductor material included in the first high refractive index layer 2 and a refractive index of light having a wavelength of 570 nm of ZnS included in the second high refractive index layer 4. A dielectric material or an oxide semiconductor material having a low refractive index of light at 570 nm is included. The light refractive index of the dielectric material or oxide semiconductor material included in the low refractive index layer at a wavelength of 570 nm is the light refractive index of the above material included 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 and more preferably 0.4 or more, respectively.

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 oxide semiconductor material contained in the low refractive index layer is MgF ₂ , SiO ₂ , AlF ₃ , CaF ₂ , CeF ₃ , CdF ₃ , LaF ₃ , LiF, NaF, Nad, 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 an oxide semiconductor material is inter _alia, is _{_{_{_{MgF 2, SiO 2, CaF 2}}}} , CeF 3, LaF 3, LiF, NaF, NdF 3, Na 3 AlF 6, Al 2 O 3, MgO or 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, a thermal CVD method or the like. From the viewpoint of easiness of film formation, 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 deposition method by placing a mask having a desired pattern on the deposition surface; It may be a patterned layer.

1-7) Third High Refractive Index Layer As described above, in the transparent conductor 100 of the present invention, the light transmittance (optical admittance) of the conductive region a of the transparent conductor is further adjusted on the low refractive index layer. A third high refractive index layer may be included. The third high refractive index layer may be formed only in the conductive region a of the transparent conductor 100, or may be formed in both the conductive region a and the insulating region b of the transparent conductor 100.

The third high refractive index layer preferably contains 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 of 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 100 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 included 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 metal sulfide. Examples of the metal oxide or metal sulfide include the metal oxide or metal sulfide 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 metal sulfide, or may contain two or more kinds.

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 within the above range, the optical admittance of the conductive region a of the transparent conductor 100 is sufficiently adjusted. The thickness of the third high refractive index layer is measured with an ellipsometer.

The film 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.

1-8) Antisulfurization layer As described above, in the transparent conductor of the present invention, one or both of the first high refractive index layer 2 and the second high refractive index layer 4 contain ZnS. Therefore, between the layer containing ZnS and the transparent metal film, specifically, between the first high refractive index layer 2 and the transparent metal film 3, or between the transparent metal film 3 and the second high refractive index layer 4. Between them, a sulfidation preventing layer for preventing sulfidation of the transparent metal film 3 may be included. When the above-mentioned underlayer is included between the first high refractive index layer 2 and the transparent metal film 3, it is preferable that an antisulfurization layer is included between the first high refractive index layer 2 and the underlayer. . The sulfidation prevention layer may be formed only in the conductive region a of the transparent conductor 100, or may be formed in both the conductive region a and the insulating region b.

When the transparent metal film 3 and the layer containing ZnS (the first high-refractive index layer 2 or the second high-refractive index layer 4) are formed adjacent to each other, When the refractive index layer 4 is formed, the metal in the transparent metal film is sulfided to form a metal sulfide, which may reduce the light transmittance of the transparent conductor. On the other hand, when an antisulfurization layer is included between the first high refractive index layer 2 and the transparent metal film 3 or between the transparent metal film 3 and the second high refractive index layer 4, the metal sulfide Generation is suppressed.

The sulfidation prevention layer may be a layer containing metal oxide, metal nitride, metal fluoride, or Zn. Only one of these may be contained in the antisulfurization layer, or two or more of them may be contained.

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, 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 , WO ₃ , etc. 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 , YF _{3 and the} like. .
Examples of the metal nitride include Si ₃ N ₄ , AlN, and the like.

The thickness of the sulfidation preventing layer is not particularly limited as long as the transparent metal film 3 can be prevented from being sulfided when the transparent metal film 3 is formed or when the second high refractive index layer 4 is formed. . However, ZnS contained in the first high refractive index layer 2 and the second high refractive index 4 has high affinity with the metal contained in the transparent metal film 3. Therefore, when the thickness of the sulfidation prevention layer is very thin, a portion where the transparent metal film 3 and the first high refractive index layer 2 or the transparent metal film 3 and the second high refractive index layer 4 are in contact with each other is generated, and the adhesion between the layers Easy to increase. That is, the antisulfurization layer is preferably relatively thin, preferably 0.1 nm to 10 nm, more preferably 0.5 nm to 5 nm, and even more preferably 1 nm to 3 nm. The thickness of the antisulfurization layer is measured with an ellipsometer.

The anti-sulfurization 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, a thermal CVD method or the like.

When the antisulfurization layer is a layer patterned into a desired shape, the patterning method is not particularly limited. The sulfidation prevention layer 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 film formation surface; patterned by a known etching method It may be a layer formed.

2. Optical Admittance of Transparent Conductor In the transparent conductor 100 of the present invention, the transparent metal film 3 is sandwiched between the first high refractive index layer 2 and the second high refractive index layer 4. As a result, the reflection of the surface of the region including the transparent metal film 3; that is, the conduction region a is suppressed, and the light transmittance of the conduction region a is increased.

The reflectance R of the surface of the transparent conductor (conducting 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 equivalent admittance Y of the surface of the transparent conductor. _Determined from _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 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 | Y _env −Y _E | is to 0, the lower the reflectance R of the surface of the transparent conductor (conduction region a).

The optical admittance Y _env of the medium is obtained from the ratio (H / E) of the electric field strength and the magnetic field strength, and is the same as the refractive index n _{env of the} medium. On the other hand, the equivalent admittance Y _E is determined from the optical admittance Y of the layers constituting the transparent conductor. For example, when the transparent conductor (conductive region a) is composed of one is 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 is a laminate, the optical admittance Y _x (E _x H _x ) of the laminate from the first layer to the x layer is the laminate from the first layer to the (x−1) layer. It is represented by the product of the optical admittance Y _x-1 (E _x-1 H _x-1 ) of the body and a specific matrix; specifically, it is obtained by the following formula (1) or formula (2).

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.

FIG. 4A shows a transparent conductor (transparent substrate / first high refractive index layer (ZnS—SiO ₂ ) / underlayer (Mo) / transparent metal film (Ag alloy) / second high refractive index layer of Example 1 described later. shows the admittance locus of wavelength 570nm conductive region a transparent conductor) with a (ZnS-SiO _2). 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 addition, in the transparent conductor of Example 1, since the thickness of a base layer is thin enough, the optical admittance can be disregarded.

In Figure 4A, the final coordinates of the admittance locus is equivalent admittance Y _E conductive region a. The distance between the coordinates (x _E , y _E ) of the equivalent admittance Y _E and the admittance coordinates (n _env , 0) (not shown) of the medium on which the light is incident is the surface of the conductive region a of the transparent conductor. It is proportional to the reflectance R of

A transparent metal film generally has a large imaginary value of optical admittance. Therefore, when a transparent metal film is laminated directly on a transparent substrate, the admittance locus greatly moves in the vertical axis (imaginary part) direction. FIG. 5A shows an admittance locus of a transparent conductor having a transparent substrate / transparent metal film / high refractive index layer in this order, and FIG. 5B shows an admittance locus of the transparent conductor having a wavelength of 450 nm, a wavelength of 570 nm, and a wavelength of 700 nm. Show the trajectory. As shown in FIG. 5A, when a transparent metal film is laminated directly on a transparent substrate, the admittance locus in the direction of the vertical axis (imaginary part) from the start point of the admittance locus (the admittance coordinates (about 1.5,0) of the transparent substrate). Moves greatly, and the absolute value of the imaginary part of the admittance coordinates becomes very large. When the absolute value of the imaginary part of the admittance coordinates increases, the equivalent admittance Y _E approaches the admittance coordinates (n _env , 0) of the medium on which light is incident even if a high refractive index layer is laminated on the transparent metal film. hard.

Further, as shown in FIG. 5A, when a transparent metal film is directly laminated on a transparent substrate, the admittance locus is less likely to be line symmetric about the horizontal axis of the graph. If the admittance locus at a specific wavelength (570 nm in the present invention) is not line symmetric about the horizontal axis of the graph, as shown in FIG. 5B, equivalent admittance Y _{E at} other wavelengths (for example, 450 nm and 700 nm). The coordinates of are easy to shake greatly. For this reason, a wavelength region in which the reflectance R cannot be sufficiently reduced occurs.

On the other hand, as shown in FIG. 4A, when the transparent metal film is sandwiched between layers having a high refractive index (first high refractive index layer and second high refractive index layer), the first high refractive index layer The coordinates of the imaginary part of the admittance locus greatly move in the positive direction. And even if an admittance locus | trajectory largely moves to the negative direction of an imaginary part by a transparent metal film, the absolute value of an imaginary part becomes difficult to become large. In addition, since the coordinates of the imaginary part of the admittance locus are largely moved again in the positive direction by the second high refractive index layer disposed on the other side of the transparent metal film, the equivalent admittance Y _E is applied to the medium on which the light is incident. Close to admittance coordinates (n _env , 0).

Furthermore, when the transparent metal film is sandwiched between layers having a high refractive index (the first high refractive index layer and the second high refractive index layer), the admittance locus tends to be line symmetric about the horizontal axis of the graph. As a result, at any wavelength, the equivalent admittance Y _E is close to the admittance coordinates (n _env , 0) of the medium on which the light is incident.

Here, in the transparent conductor of the present invention, the optical admittance at a wavelength of 570 nm on the surface of the transparent metal film on the high refractive index layer side is Y1 (= x ₁ + ii ₁ ), and the wavelength on the surface of the transparent metal film on the intermediate layer side 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 following relational expression holds between the admittance Y at the interface of each layer 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 film is increased, the electric field strength E is decreased and the electric field loss (light absorption) 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 are preferably 1.6 or more, more preferably 1.8 or more, and further preferably 2.0 or more. In particular, x ₁ is 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 in such a thickness of the first high refractive index layer. x ₂ is the refractive index of the values and the transparent metal film x _1, is adjusted by the thickness or the like of the first transparent metal film. 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.

Further, as described above, the admittance trajectory is preferably line symmetric about the horizontal axis of the graph. 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 optical admittance of the transparent metal film has a large imaginary part value, and the admittance locus greatly moves in the vertical axis (imaginary part) direction. Therefore, if y ₁ is sufficiently large, the absolute value of the imaginary part of the admittance coordinates fit in appropriate range, the admittance locus is likely to be axisymmetric. 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 in the member or environment (medium) in contact with the surface on the second high refractive index layer side of the transparent conductor. Distance from equivalent admittance coordinates (n _env , 0) ((x _E −n _env ) ² + (y _E ) ² ) ^0.5 is preferably less than 0.5, more preferably 0.3 or less It is. When the distance is less than 0.5, the reflectance Ra of the surface of the conduction region _a is sufficiently small, and the light transmittance of the conduction region a is increased.

Further, when the transparent metal film 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. When the distance between the equivalent admittance coordinates of the conduction region a and the equivalent admittance coordinates of the insulation region b is short, the pattern composed of the conduction region a and the insulation region b is difficult to be visually recognized. In addition, it is preferable that | (x _env −x _b ) ² + (y _env −y _b ) ² − (x _env −x _E ) ² − (y _env −y _E ) ² | When the value is 0.01 or less, it is difficult to visually recognize both the conduction region a and the insulation region b.

The coordinates of the equivalent admittance _{Y E} of the conducting areas a, sufficiently close to the coordinates of the equivalent admittance _{Y b} of the insulating region b; that is _{_{^{_{((x E -x b) 2}}}} + (y E -y b) 2) 0. ^In order to make ⁵ smaller, (i) the admittance locus of the conduction region a is symmetrical with respect to the horizontal axis of the graph, and (ii) the insulation region b includes only a transparent substrate. Is preferred. When admittance locus conductive region a is in line symmetry about the horizontal axis of the graph, the coordinate of Y _E is because approaching the naturally transparent substrate 1 admittance.

3. Regarding physical properties of transparent conductor The average transmittance of light having a wavelength of 400 to 1000 nm of the transparent conductor of the present invention is preferably 80% or more, more preferably 83% or more, and further preferably 85% or more. When the transparent metal film 3 is patterned and the transparent conductor 100 includes the conductive region a and the insulating region b, the average transmittance is 80% or more in any region. 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.

In particular, the average transmittance of light having a wavelength of 450 to 800 nm of the transparent conductor is preferably 83% or more, more preferably 85% or more, and even 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 85% or more, the transparent conductor can be applied to applications requiring high transparency to visible light.

On the other hand, the average absorptance of light having a wavelength of 400 nm to 800 nm of the transparent conductor is preferably 10% or less, more preferably 8% or less, and still more preferably in both the conduction region a and the insulation region b. 7% or less. Further, the maximum value of the light absorptance of the transparent conductor having a wavelength of 450 nm to 800 nm is preferably 15% or less, more preferably 10% or less, in any of the conduction region a and the insulation region b. Preferably it is 9% or less. On the other hand, the average reflectance of light with a wavelength of 500 nm 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, average reflectance, and average reflectance are preferably the average transmittance, average reflectance, and average 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 average transmittance and the average 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 average transmittance and the average 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).

In addition, when the conductive region a and the insulating region b are included in the transparent conductor 100, it is preferable that the reflectance of the conductive region a and the reflectance of the insulating region b are approximated. Specifically, the difference ΔR between the luminous reflectance of the conductive region a and the luminous reflectance of the insulating region b is preferably 3% or less, more preferably 1% or less, and even more 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).

In addition, when the transparent conductor 100 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 electric resistance value of the conduction region a is adjusted by the thickness of the transparent metal film. 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.

4). Applications of transparent conductors The above-mentioned transparent conductors include various types of displays such as liquid crystal, plasma, organic electroluminescence, field emission, touch panels, mobile phones, electronic paper, various solar cells, various electroluminescent dimming elements, etc. It can be preferably used for a substrate of an optoelectronic device.

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.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by this.

[Example 1]
A first high refractive index layer (ZnS-SiO ₂ ) / underlayer (Mo) / transparent metal film (APC alloy) / second high refractive index on a film made of cycloolefin polymer (thickness 100 μm) by the following method. Layers (ZnS—SiO ₂ ) were stacked in this order. Thereafter, the laminate was patterned by the following method. The thickness of each layer is described in J. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer. However, the average thickness of the underlayer was calculated from the film formation rate at the nominal value of the manufacturer of the sputtering apparatus. The spectral characteristic of the obtained transparent conductor is shown in FIG. 4B.

(First high refractive index layer (ZnS—SiO ₂ ))
On the transparent substrate, using a magnetron sputtering apparatus of Osaka Vacuum Co., ZnS—SiO ₂ at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, film formation rate 3.0 Å / s. Was RF sputtered. The target-substrate distance was 90 mm.
The ratio (volume ratio) between ZnS and SiO ₂ was 95: 5, and the refractive index of the first high refractive index layer was 2.14.

(Underlayer (Mo))
On the first high-refractive index layer, L-430S-FHS manufactured by Anelva is used, and Ar is 20 sccm, sputtering pressure is 0.5 Pa, room temperature, target-side power is 50 W, and deposition rate is 0.4 Å / s. Sputtered. The target-substrate distance was 86 mm.

(Transparent metal film (APC alloy))
APC alloy (manufactured by Furuya Metal Co., Ltd.) was RF-sputtered using L-430S-FHS manufactured by Anerva Co., Ar 20 sccm, sputtering pressure 0.3 Pa, room temperature, target-side power 100 W, and deposition rate 2.5 Å / s. The target-substrate distance was 86 mm.

(Second high refractive index layer (ZnS-SiO ₂ ))
Similar to the first high refractive index layer, a second high refractive index layer was formed on the transparent metal film. The ratio (volume ratio) between ZnS and SiO ₂ was 95: 5, and the refractive index of the first high refractive index layer was 2.14.

(Layer patterning)
A resist layer is formed in a pattern on the obtained laminate, and the first high-refractive index layer, the underlayer, the transparent metal film, and the second high-refractive index layer are formed in the pattern shown in FIG. a) and a line-shaped insulating region b separating the same), and patterned with an ITO etching solution (produced by Hayashi Junyaku). Only the transparent substrate was included in the insulating region. The width of the line-shaped insulating region b was 16 μm.

[Example 2]
A first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (APC alloy) / second high refractive index layer (ZnS—SiO ₂ ) were laminated in this order on a Konica Minolta TAC film (thickness 40 μm). .
Each layer was formed in the same manner as in Example 1 except that the base layer was not formed and the ratio (volume ratio) of ZnS and SiO _{2 of} the first high refractive index layer and the second high refractive index layer was 80:20. A film was formed.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 6 shows the spectral characteristics of the obtained transparent conductor.

[Example 3]
On a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (APC-SR alloy) / second high refractive index layer (ZnS—SiO 2) ₂ ) were laminated in this order.
The first high refractive index layer and the second high refractive index layer were formed in the same manner as in Example 1 except that the ratio (volume ratio) of ZnS and SiO ₂ was 90:10.
As the transparent metal film, each layer was formed in the same manner as in Example 2 except that the target during film formation was changed to an APC-SR alloy (manufactured by Furuya Metal Co., Ltd.).
The obtained laminate was patterned in the same manner as in Example 1. FIG. 7 shows the spectral characteristics of the obtained transparent conductor.

[Example 4]
On a film made of polycarbonate (thickness 100 μm), first high refractive index layer (ZnS—SiO ₂ ) / underlayer (Pd) / transparent metal film (APC-SR alloy) / second high refractive index layer (ZnS—SiO 2) ₂ ) were laminated in this order.
The first high refractive index layer and the second high refractive index layer were formed in the same manner as in Example 2.
The underlayer and the transparent metal film were formed by the following methods, respectively.
The obtained laminate was patterned in the same manner as in Example 1. The spectral characteristics of the obtained transparent conductor are shown in FIG.

(Underlayer (Pd))
Using a magnetron sputtering apparatus (MSP-1S) manufactured by Vacuum Device Inc., palladium was deposited for 0.4 seconds to form growth nuclei with an average thickness of 0.2 nm.

(Transparent metal film (APC-SR))
Using a counter sputtering machine manufactured by FTS Corporation, Ag was counter sputtered at an Ar of 20 sccm, a sputtering pressure of 0.5 Pa, a room temperature, a target power of 150 W, and a film formation rate of 14 K / s. The target-substrate distance was 90 mm.

[Example 5]
A first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (APC-SR alloy) / second high refractive index layer (ZnS—SiO ₂ ) in this order on a Konica Minolta TAC film (thickness 40 μm). Laminated.
The transparent metal film was formed in the same manner as in Example 4.
The first high refractive index layer and the second high refractive index layer were formed in the same manner as in Example 1 except that the ratio (volume ratio) of ZnS and SiO ₂ was 70:30.
The obtained laminate was patterned in the same manner as in Example 1. The spectral characteristics of the obtained transparent conductor are shown in FIG.

[Example 6]
A first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (APC-TR alloy) / second high refractive index layer (ZnS—SiO ₂ ) is formed on a film (thickness 100 μm) made of cycloolefin polymer. Laminated in order.
The first high refractive index layer and the second high refractive index layer were formed in the same manner as in Example 2.
The transparent metal film was formed in the same manner as in Example 4 except that the target at the time of film formation was changed to APC-TR alloy.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 10 shows the spectral characteristics of the obtained transparent conductor.

[Example 7]
On a transparent substrate (thickness 50 μm) made of glass, first high refractive index layer (ZnO) / underlayer (Pd) / transparent metal film (APC-TR alloy) / second high refractive index layer (ZnS—SiO ₂ ) Were stacked in this order.
The first high refractive index layer was formed by the following method.
The underlayer was formed by the same method as in Example 4.
The transparent metal film was formed in the same manner as in Example 4 except that the target during film formation was APC-TR (manufactured by Furuya Metal Co., Ltd.).
The second high refractive index layer was formed in the same manner as in Example 2. The obtained laminate was patterned in the same manner as in Example 1.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 11 shows the spectral characteristics of the obtained transparent conductor.

(First high refractive index layer (ZnO))
Using a magnetron sputtering apparatus of Osaka Vacuum Co., ZnO was RF-sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 1.1 liters / s. The target-substrate distance was 90 mm. The refractive index of light with a wavelength of 570 nm of ZnO was 2.01, and the refractive index of light with a wavelength of 570 nm of the first high refractive index layer was also 2.01.

[Example 8]
On Konica Minolta TAC film (thickness 60 μm), first high refractive index layer (ITO) / underlayer (Pd) / transparent metal film (Ag—Bi—Ge—Au alloy) / second high refractive index layer (ZnS) -SiO ₂ ) were sequentially laminated.
The first high refractive index layer was formed by the following method.
The underlayer was formed by the same method as in Example 4.
For the transparent metal film, the target at the time of film formation was GBR15 (manufactured by Kobelco Research Institute: Ag (98.35 at%) / Bi (0.35 at%) / Ge (0.3%) / Au (1.0 at%)). A film was formed in the same manner as in Example 4 except that.
The second high refractive index layer was formed by the same method as in Example 2.
The obtained laminate was patterned in the same manner as in Example 1. The spectral characteristics of the obtained transparent conductor are shown in FIG.

(First high refractive index layer (ITO))
Using Anelva L-430S-FHS, ITO was DC sputtered at Ar 20 sccm, O ₂ 5 sccm, sputtering pressure 0.3 Pa, room temperature, target-side power 150 W, and deposition rate 2.0 Å / s. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of ITO was 2.12, and the refractive index of light with a wavelength of 570 nm of the first high refractive index layer was also 2.12. ITO _{_{_{is, In 2 O 3: SnO 2}}} = 90: was 10 (weight% ratio).

[Example 9]
On a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), first high refractive index layer (Nb ₂ O ₅ ) / underlayer (Pd) / transparent metal film (Ag—Bi—Ge—Au alloy) / A second high refractive index layer (ZnS—SiO ₂ ) was laminated in order.
The first high refractive index layer was formed by the following method.
The underlayer was formed by the same method as in Example 4.
The transparent metal film and the second high refractive index layer were formed in the same manner as in Example 8.
The obtained laminate was patterned in the same manner as in Example 1. The spectral characteristics of the obtained transparent conductor are shown in FIG.

(First high refractive index layer (Nb ₂ O ₅ ))
Nb ₂ O ₅ was DC sputtered at 20 sccm Ar, 1 sccm O ₂ , sputtering pressure 0.5 Pa, room temperature, target side power 150 W, deposition rate 1.2 Å / s using L-430S-FHS manufactured by Anerva. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of Nb ₂ O ₅ was 2.31, and the refractive index of light with a wavelength of 570 nm of the first high refractive index layer was also 2.31.

[Example 10]
On a Konica Minolta TAC film (thickness 60 μm), first high refractive index layer (ZrO ₂ ) / underlayer (Pd) / transparent metal film (Ag—Bi alloy) / second high refractive index layer (ZnS—SiO ₂₎ ) In order.
The first high refractive index layer was formed by the following method.
The underlayer was formed by the same method as in Example 4.
The transparent metal film was formed by the same method as in Example 1 except that the film formation target was GB100 (manufactured by Kobelco Research Institute: Ag (99.0 at%) / Bi (1.0 at%)).
The second high refractive index layer was formed in the same manner as in Example 2.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 14 shows the spectral characteristics of the obtained transparent conductor.

(First high refractive index layer (ZrO ₂ ))
Using Arnelva L-430S-FHS, ZrO ₂ was RF sputtered at Ar 20 sccm, O ₂ 1 sccm, sputtering pressure 0.5 Pa, room temperature, target-side power 150 W, and deposition rate 0.5 Å / s. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of ZrO ₂ was 2.05, and the refractive index of light with a wavelength of 570 nm of the first high refractive index layer was also 2.05.

[Example 11]
On a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), first high refractive index layer (Ta ₂ O ₅ ) / underlayer (Pd) / transparent metal film (Ag—Bi alloy) / second high refraction The rate layer (ZnS—SiO ₂ ) was sequentially laminated.
The first high refractive index layer was formed by the following method.
The underlayer was formed by the same method as in Example 4.
The transparent metal film was formed in the same manner as in Example 4 except that the film formation target was GB100 (manufactured by Kobelco Research Institute: Ag (99.0 at%) / Bi (1.0 at%)).
The second high refractive index layer was formed in the same manner as in Example 2.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 15 shows the spectral characteristics of the obtained transparent conductor.

(First high refractive index layer (Ta ₂ O ₅ ))
The oxygen was introduced so that the total pressure in the vapor deposition apparatus would be 2.0 × 10 ⁻² Pa by Genen 1300 of Optorun, and the electron was not ion-assisted Ta ₂ O ₅ at 400 mA and a film formation rate of 4 Å / s. Beam (EB) deposition was performed. The refractive index of light with a wavelength of 570 nm of Ta ₂ O ₅ was 2.16, and the refractive index of the first high refractive index layer was also 2.16.

[Example 12]
A first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (APC alloy) / second high refractive index layer (ITO) was laminated in this order on a Konica Minolta TAC film (thickness 40 μm).
The first high refractive index layer was formed in the same manner as in Example 2.
The transparent metal film was formed in the same manner as in Example 1.
The second high refractive index layer was formed in the same manner as the first high refractive index layer of Example 8.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 16 shows the spectral characteristics of the obtained transparent conductor.

[Example 13]
A first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (APC-TR alloy) / second high refractive index layer (IZO) were laminated in this order on a transparent substrate (thickness 50 μm) made of glass.
The first high refractive index layer and the transparent metal film were formed in the same manner as in Example 6.
The second high refractive index layer was formed by the following method.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 17 shows the spectral characteristics of the obtained transparent conductor.

(Second high refractive index layer (IZO))
Using an Anelva L-430S-FHS, IZO was RF sputtered at Ar 20 sccm, O ₂ 5 sccm, sputtering pressure 0.3 Pa, room temperature, target-side power 300 W, and deposition rate 2.2 L / s. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of IZO was 2.05, and the refractive index of light with a wavelength of 570 nm of the second high refractive index layer was also 2.05. IZO was In ₂ O ₃ : ZnO = 90: 10.

[Example 14]
A first high refractive index layer (ZnS-SiO ₂ ) / transparent metal film (APC-TR alloy) / second high refractive index layer (GZO) were laminated in this order on a film made of cycloolefin polymer (thickness: 100 μm). .
The first high refractive index layer and the transparent metal film were formed in the same manner as in Example 6.
The second high refractive index layer was formed by the following method.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 18 shows the spectral characteristics of the obtained transparent conductor.

(Second high refractive index layer (GZO))
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., GZO was RF-sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 1.1 Å / s. The target-substrate distance was 90 mm.
The refractive index of light with a wavelength of 570 nm of GZO was 2.04, and the refractive index of light with a wavelength of 570 nm of the second high refractive index layer was also 2.04. GZO _{_{is, Ga 2 O 3: ZnO =}} 5: was 95.

[Example 15]
A first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (APC-SR alloy) / second high refractive index layer (Nb ₂ O ₅ ) are laminated in this order on a polycarbonate film (thickness: 100 μm). did.
The first high refractive index layer and the transparent metal film were formed in the same manner as in Example 4.
The second high refractive index layer was formed in the same manner as the first high refractive index layer of Example 9.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 19 shows the spectral characteristics of the obtained transparent conductor.

[Example 16]
On a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (Ag—Bi—Ge—Au alloy) / second high refractive index layer (TiO ₂ ) was deposited in this order.
The first high refractive index layer was formed in the same manner as in Example 2, and the transparent metal film was formed in the same manner as in Example 8.
The second high refractive index layer was formed by the following method.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 20 shows the spectral characteristics of the obtained transparent conductor.

(Second high refractive index layer (TiO ₂ ))
The Optorun's Gener 1300, 320 mA, the TiO ₂ at a deposition rate of 3 Å / s, and electron beam (EB) vapor deposition with ion assist. The ion beam was irradiated at a current of 500 mA, a voltage of 500 V, and an acceleration voltage of 400 V. In the ion beam apparatus, O ₂ gas: 50 sccm and Ar gas: 8 sccm were introduced. The refractive index of light with a wavelength of 570 nm of TiO ₂ was 2.35, and the refractive index of light with a wavelength of 570 nm of the second high refractive index layer was also 2.35.

[Example 17]
A first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (APC-TR alloy) / second high refractive index layer (IGZO) were formed in this order on a Konica Minolta TAC film (thickness 40 μm). .
The first high refractive index layer was formed in the same manner as in Example 2, and the transparent metal film was formed in the same manner as in Example 6.
The second high refractive index layer was formed by the following method.
The obtained laminate was patterned in the same manner as in Example 1. FIG. 21 shows the spectral characteristics of the obtained transparent conductor.

(Second high refractive index layer (IGZO))
Using Anelva L-430S-FHS, IGZO was RF sputtered at Ar 20 sccm, O ₂ 5 sccm, sputtering pressure 0.3 Pa, room temperature, target-side power 300 W, and deposition rate 2.2 L / s. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of IGZO was 2.09, and the refractive index of light with a wavelength of 570 nm of the second high refractive index layer was also 2.09. IGZO was set to O: Zn: Ga: In = 48.4: 13.2: 24.9: 13.6 (at% ratio).

[Example 18]
A first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (APC alloy) / second high refractive index layer (ZnS—SiO ₂ ) are laminated in this order on a film (thickness 100 μm) made of a cycloolefin polymer. did.
The first high refractive index layer and the second high refractive index layer were formed in the same manner as in Example 2.
The transparent metal film was formed in the same manner as in Example 4 except that the film formation target was APC-SR (manufactured by Furuya Metal Co., Ltd.).
The spectral characteristics of the obtained transparent conductor are shown in FIG.

[Example 19]
On a film made of polycarbonate (thickness 100 μm), first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (APC-SR alloy) / second high refractive index layer (ZnS—SiO ₂ ) / low refractive index Layer (SiO ₂ ) / third high refractive index layer (Bi ₂ O ₃ ) were laminated in this order.
The first high refractive index layer, the transparent metal film, and the second high refractive index layer were formed in the same manner as in Example 4.
The low refractive index layer and the third high refractive index layer were formed by the following method.
FIG. 23 shows the spectral characteristics of the obtained transparent conductor.

(Low refractive index layer (SiO ₂ ))
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., SiO ₂ was RF-sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 300 W, and deposition rate 1.6 Å / s. The target-substrate distance was 90 mm. The refractive index of light with a wavelength of 570 nm of SiO ₂ was 1.46, and the refractive index of light with a wavelength of 570 nm of the low refractive index layer was also 1.46.

(Third high refractive index layer (Bi ₂ O ₃ ))
Using a magnetron sputtering apparatus of Osaka Vacuum Co., Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, Bi ₂ O ₃ was RF sputtered. The target-substrate distance was 90 mm. Bi ₂ O ₃ had a refractive index of light of 570 nm wavelength of 1.95, and the third high refractive index layer also had a refractive index of light of wavelength 570 nm of 1.95.

[Example 20]
On a film made of glass (thickness 50 μm), first high refractive index layer (ZnO) / underlayer (Pd) / transparent metal film (APC-TR alloy) / second high refractive index layer (ZnS—SiO ₂ ) / A low refractive index layer (SiO ₂ ) / third high refractive index layer (ZnS) were laminated in this order.
The first high refractive index layer, the underlayer, the transparent metal film, and the second high refractive index layer were formed in the same manner as in Example 7.
The low refractive index layer was formed by the same method as in Example 19.
The third high refractive index layer was formed by the following method.
The spectral characteristics of the obtained transparent conductor are shown in FIG.

(Third high refractive index layer (ZnS))
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., ZnS was RF sputtered at Ar 20 sccm, O ₂ 0 sccm, sputtering pressure 0.1 Pa, room temperature, target-side power 150 W, and deposition rate 3.8 Å / s. The target-substrate distance was 90 mm. The refractive index of light with a wavelength of 570 nm of ZnS was 2.37, and the refractive index of light with a wavelength of 570 nm of the third high refractive index layer was also 2.37.

[Example 21]
On a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), first high refractive index layer (ITO) / underlayer (Pd) / transparent metal film (Ag—Bi—Ge—Au alloy) / second high A refractive index layer (ZnS—SiO ₂ ) was laminated in this order.
The first high refractive index layer, the underlayer, the transparent metal film, and the second high refractive index layer were formed in the same manner as in Example 8.
FIG. 25 shows the spectral characteristics of the obtained transparent conductor.

[Example 22]
On a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), first high refractive index layer (TiO ₂ ) / transparent metal film (Ag—Bi alloy) / second high refractive index layer (ZnS—SiO ₂ ) Were stacked in this order.
The first high refractive index layer was formed in the same manner as the second high refractive index layer of Example 16.
The transparent metal film was formed in the same manner as in Example 11.
The second high refractive index layer was formed in the same manner as in Example 2.
FIG. 26 shows the spectral characteristics of the obtained transparent conductor.

[Example 23]
A first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (Ag—Bi alloy) / second high refractive index layer (ITO) were laminated in this order on a Konica Minolta TAC film (thickness 40 μm).
The first high refractive index layer and the transparent metal film were formed in the same manner as in Example 17.
The second high refractive index layer was formed in the same manner as in Example 12.
FIG. 27 shows the spectral characteristics of the obtained transparent conductor.

[Example 24]
A first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (Ag—Ge alloy) / second high refractive index layer (IZO) were laminated in this order on a glass film (thickness 50 μm).
The first high refractive index layer was formed in the same manner as in Example 2.
The transparent metal film was formed in the same manner as in Example 4 except that the film formation target was an Ag (99.0 at%)-Ge (1.0 at%) alloy.
The second high refractive index layer was formed in the same manner as in Example 13.
The spectral characteristics of the obtained transparent conductor are shown in FIG.

[Example 25]
A first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (Ag—Pd alloy) / second high refractive index layer (GZO) were laminated in this order on a film (thickness 100 μm) made of cycloolefin polymer. .
The first high refractive index layer was formed in the same manner as in Example 2.
The transparent metal film was formed by the same method as in Example 1 except that the deposition target was an Ag (99.0 at%)-Pd (1.0 at%) alloy.
The second high refractive index layer was formed in the same manner as in Example 14.
The spectral characteristic of the obtained transparent conductor is shown in FIG.

[Example 26]
On a film made of polycarbonate (thickness 100 μm), first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (Ag—Cu alloy) / second high refractive index layer (Nb ₂ O ₅ ) / low refractive index Layer (SiO ₂ ) / third high refractive index layer (ZnS) were laminated in this order.
The first high refractive index layer and the second high refractive index layer were formed in the same manner as in Example 15.
The transparent metal film was formed in the same manner as in Example 4 except that the film formation target was an Ag (95.0 at%)-Cu (5.0 at%) alloy.
The low refractive index layer and the third high refractive index layer were formed in the same manner as in Example 20.
FIG. 30 shows the spectral characteristics of the obtained transparent conductor.

[Example 27]
On a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (Ag—Nd alloy) / second high refractive index layer (TiO ₂ ) Were stacked in this order.
The first high refractive index layer and the second high refractive index layer were formed in the same manner as in Example 16.
The transparent metal film was formed in the same manner as in Example 4 except that the deposition target was an Ag (99.0 at%)-Nd (1.0 at%) alloy.
FIG. 31 shows the spectral characteristics of the obtained transparent conductor.

[Example 28]
A first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (APC-TR alloy) / second high refractive index layer (IGZO) was laminated in this order on a Konica Minolta TAC film (thickness 40 μm).
The first high refractive index layer and the second high refractive index layer were formed in the same manner as in Example 17.
The transparent metal film was formed in the same manner as in Example 6.
The spectral characteristics of the obtained transparent conductor are shown in FIG.

[Example 29]
On a film made of polycarbonate (thickness 100 μm), first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (Ag—Au alloy) / second high refractive index layer (Nb ₂ O ₅ ) / low refractive index Layer (SiO ₂ ) / third high refractive index layer (ZnS) were laminated in this order.
The first high refractive index layer, the second high refractive index layer, the low refractive index layer, and the third high refractive index layer were formed in the same manner as the respective layers of Example 26.
The transparent metal film was formed in the same manner as in Example 4 except that the film formation target was an Ag (98.0 at%)-Au (2.0 at%) alloy.

[Example 30]
On a film made of cycloolefin polymer (thickness 100 μm), first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (APC-TR alloy) / sulfurization preventive layer (ZnO) / second high refractive index layer ( ZnS—SiO ₂ ) were laminated in this order. The obtained laminate was patterned in the same manner as in Example 1.
The first high refractive index layer and the second high refractive index layer were formed in the same manner as in Example 2.
The transparent metal film was formed in the same manner as in Example 6.
The sulfidation preventing layer was formed in the same manner as the first high refractive index layer of Example 7.

[Example 31]
On Konica Minolta TAC film (thickness 40 μm), first high refractive index layer (ZnS—SiO ₂ ) / sulfurization preventive layer (ZnO) / transparent metal film (APC alloy) / second high refractive index layer (ZnS—SiO 2) ₂ ) were laminated in this order. The obtained laminate was patterned in the same manner as in Example 1.
The first high refractive index layer and the second high refractive index layer were formed in the same manner as in Example 2.
The transparent metal film was formed in the same manner as in Example 6.
The sulfidation preventing layer was formed in the same manner as the first high refractive index layer of Example 7.

[Example 32]
On a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), first high refractive index layer (ZnS—SiO ₂ ) / first antisulfuration layer (ZnO) / transparent metal film (APC-TR alloy) / A disulfide prevention layer (ZnO) / second high refractive index layer (ZnS—SiO ₂ ) were laminated in this order. The obtained laminate was patterned in the same manner as in Example 1.
The first high refractive index layer and the second high refractive index layer were formed in the same manner as in Example 2.
The transparent metal film was formed in the same manner as in Example 6.
The sulfidation preventing layer was formed in the same manner as the first high refractive index layer of Example 7.

[Example 33]
On a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), first high refractive index layer (ZnS compound) / first antisulfuration layer (GZO) / transparent metal film (APC-TR alloy) / second An antisulfurization layer (GZO) / second high refractive index layer (SGZO) / third high refractive index layer (ITO) were laminated in this order. The obtained laminate was patterned in the same manner as in Example 1.

The first high-refractive index layer and the second high-refractive index layer each have a ZnS compound (ZnS.ZnO.In ₂ O ₃ .Ga ₂ O ₃ .SiO ₂ (O: Zn: In: Ga: S: Si (at% ratio) = 35: 33: 5: 9: 17: 1)) and SGZO (O: S: Zn: Ga (at% ratio)) = 48.4: 0.8: 45. 2: 5.6) A film was formed in the same manner as the first high refractive index layer in Example 1.
The sulfidation preventing layer was formed in the same manner as the second high refractive index layer of Example 14.
The transparent metal film was formed in the same manner as in Example 6.
The third high refractive index layer was formed in the same manner as the first high refractive index layer of Example 8.
The spectral characteristic of the obtained transparent conductor is shown in FIG.

[Example 34]
On a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm), first high refractive index layer (ZnS compound) / first antisulfuration layer (IGZO) / transparent metal film (APC-TR alloy) / second Antisulfuration layer (IGZO) / second high refractive index layer (TIZO) / third high refractive index layer (ITO) were laminated in this order. The obtained laminate was patterned in the same manner as in Example 1.

The first high-refractive index layer and the second high-refractive index layer are targets for film formation, ZnS.ZnO.Ga ₂ O ₃ (O: Zn: Ga: S (at% ratio) = 29: 51: 4:16) and TIZO (O: Zn: In: Sn (at% ratio) = 48: 32: 16: 4) were formed in the same manner as the first high refractive index layer of Example 1.
The sulfidation preventing layer was formed in the same manner as the second high refractive index layer of Example 17.
The transparent metal film was formed in the same manner as in Example 6.
The third high refractive index layer was formed in the same manner as the first high refractive index layer of Example 8.
FIG. 37 shows the spectral characteristics of the obtained transparent conductor.

[Comparative Example 1]
A first high refractive index layer (ZnS) / transparent metal film (Ag) / second high refractive index layer (ZnS) was laminated in this order on a transparent substrate made of quartz.
The first high refractive index layer, the transparent metal film, and the second high refractive index layer were formed by the following methods, respectively.
The spectral characteristic of the obtained transparent conductor is shown in FIG.

(First high refractive index layer and second high refractive index layer (ZnS))
As the first high refractive index layer and the second high refractive index layer, films made of ZnS were formed by resistance heating using a BMC-800T vapor deposition machine manufactured by SYNCHRON, respectively. The input current value at this time was 210 A, and the film formation rate was 5 Å / s.

(Transparent metal film (Ag))
On the first high refractive index layer, a silver film having a thickness of 12 nm was formed 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 film formation rate was 5 Å / s.

[Comparative Example 2]
On a transparent substrate made of EAGLE Glass, a first high refractive index layer (ZnS) / transparent metal film (Ag) / second high refractive index layer (ZnS) were laminated in this order.
The first high refractive index layer and the second high refractive index layer were formed in the same manner as in Example 1.
The transparent metal film was formed in the same manner as in Comparative Example 1.

[Comparative Example 3]
A first high refractive index layer (Nb ₂ O ₅ ) / transparent metal film (Ag) / second high refractive index layer (IZO) were laminated in this order on a transparent substrate made of Toyobo PET (Cosmo Shine A4300 thickness 50 μm). .
Each layer was formed by the following method.
The spectral characteristics of the conduction region of the obtained transparent conductor are shown in FIG.

(First high refractive index layer (Nb ₂ O ₅ ))
Nb ₂ O ₅ was RF-sputtered using Arnelva L-430S-FHS at Ar 20 sccm, O ₂ 5 sccm, sputtering pressure 0.3 Pa, room temperature, target-side power 300 W, and deposition rate 0.74 Å / s. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of Nb ₂ O ₅ is 2.31, but the refractive index of light with a wavelength of 570 nm of the high refractive index layer is 2.35.

(Transparent metal film (Ag))
DC sputtering was performed with a small sputtering apparatus (BC4279) manufactured by Nippon Vacuum Technology Co., Ltd. At this time, the target side power was set to 200 W.

(Second high refractive index layer (IZO))
Using an Anelva L-430S-FHS, IZO was RF sputtered at Ar 20 sccm, O ₂ 5 sccm, sputtering pressure 0.3 Pa, room temperature, target-side power 300 W, and deposition rate 2.2 L / s. The target-substrate distance was 86 mm. The refractive index of light with a wavelength of 570 nm of IZO is 2.05, but the refractive index of light with a wavelength of 570 nm of the second high refractive index layer is 1.98.

[Comparative Example 4]
On Konica Minolta TAC film (transparent substrate), first high refractive index layer (ICO) / underlayer (NiCr) / transparent metal film (AgAu) / adhesion layer (NiCr) / second high refractive index layer (ICO) / Low refractive index layer (SiO ₂ ) / Fluorine-based material layer (KP801M) were laminated in this order.
The low refractive index layer was formed in the same manner as the low refractive index layer of Example 12. The other layers were formed by the following methods.

(First high refractive index layer and second high refractive index layer (ICO))
The target was formed in the same manner as the second high refractive index layer of Comparative Example 3 except that the target was made of a material (ICO) containing 10 atomic% of cerium in indium. The refractive index of light with a wavelength of 570 nm of ICO was 2.2, and the refractive indexes of light with a wavelength of 570 nm of the first high refractive index layer and the second high refractive index layer were also 2.2.

(Underlayer and adhesion layer (NiCr))
A film was formed in the same manner as the base layer (Pd) of Example 5 except that the target was NiCr.

(Transparent metal film (AgAu))
An alloy alloy L-430S-FHS, Ar 20 sccm, sputtering pressure 0.3 Pa, room temperature, target side power 100 W, film formation rate 2.5 kg / s, Ag alloy (1.5 atomic% of Au in Ag) An alloy containing 0.5 atomic% of Cu) was RF sputtered. The target-substrate distance was 86 mm.

(Fluorine material layer (KP801M))
Fluorine-based material (manufactured by Shin-Etsu Chemical Co., Ltd .: KP801M) was vapor-deposited by resistance heating with a Gener 1300 manufactured by Optorun at 190 mA and a film formation rate of 10 kg / s.

[Comparative Example 5]
A first high refractive index layer (ITO) / transparent metal film (APC) / second high refractive index layer (ITO) were laminated in this order on a transparent substrate made of Toyobo PET (Cosmo Shine A4300, thickness 50 μm).
The first high refractive index layer and the second high refractive index layer were formed in the same manner as the first high refractive index layer of Example 17, respectively.
The transparent metal film was formed by the following method.

(Transparent metal film (APC))
An alloy of L-430S-FHS manufactured by Anelva, an alloy of Ag, Pd, and Cu (Ag: Pd :) at Ar 20 sccm, sputtering pressure 0.3 Pa, room temperature, target side power 100 W, and deposition rate 2.5 Å / s. RF sputtering was performed on Cu = 99: 1: 1 (mass ratio). The target-substrate distance was 86 mm.

[Comparative Example 6]
On a transparent substrate made of Corning glass substrate (# 7059, thickness 1.1 mm), first high refractive index layer (a-GIO) / transparent metal film (Ag) / second high refractive index layer (a-GIO) ) In order.
Each layer was formed by the following method.

(First high refractive index layer and second high refractive index layer (a-GIO))
An oxide sintered body of Ga and In was DC sputtered at an electric power density of 2.2 W / cm ^{2 in} an atmosphere of 0.6 Pa of Ar gas mixed with O ₂ gas. The ratio of O ₂ gas to be introduced was 8 to 12% by volume.

(Transparent metal film (Ag))
A 4N purity Ag target was DC sputtered at an electric power density of 0.55 W / cm ^{2 in} an atmosphere of Ar gas of 0.6 Pa.

[Comparative Example 7]
On the K9 glass substrate, a first high refractive index layer (ZnS—SiO ₂ ) / transparent metal film (Ag) / second high refractive index layer (ZnS—SiO ₂ ) were laminated in this order.
Each layer was formed by the following method.
The spectral characteristics of the conduction region of the obtained transparent conductor are shown in FIG.

(First high refractive index layer and second high refractive index layer (ZnS—SiO ₂ ))
The first high refractive index layer and the second high refractive index layer were formed in the same manner as the method described in Patent Document 5 described above. Specifically, ZnS—SiO ₂ was RF sputtered by magnetron sputtering. The ratio (mass ratio) between ZnS and SiO ₂ was 80:20, and the refractive index of the first high refractive index layer was 2.14.

(Transparent metal film (Ag))
On the first high refractive index layer, an Ag target was DC sputtered in the same manner as the method described in Patent Document 5 described above.

[Evaluation]
About the transparent conductor obtained in each Example and Comparative Example, corrosivity, flexibility, light transmittance, light reflectance, light absorption rate, luminous reflectance, a * value and b * value, and The surface electrical resistance was measured. The results are shown in Tables 1 to 4. Furthermore, the optical admittance of the transparent conductor was calculated. Values are shown in Tables 5-8.

(Corrosion evaluation)
The corrosion resistance of the transparent conductors obtained in Examples and Comparative Examples was evaluated. Corrosion resistance was evaluated by the appearance after storing the transparent conductors obtained in Examples or Comparative Examples two by two in 65 ° C. and 95% Rh for 100 hours. Evaluation was based on the following criteria.
○: In the area of 30 mm × 30 mm, 0 corrosion sites with a size of 20 μm or more Δ: In the region of 30 mm × 30 mm, 1 or more and less than 10 corrosion sites with a size of 20 μm or more ×: Size in the region of 30 mm × 30 mm 10 or more corrosion spots of 20μm or more

(Flexibility evaluation)
The transparent conductors obtained in Examples and Comparative Examples were placed on a flat support member, and one end was fixed. The transparent conductor was bent into a U shape. The curvature radius of the bent portion was 5 mm. And the other end of the transparent conductor was fixed to the sliding plate arrange | positioned in parallel with the supporting member. The sliding plate was reciprocated 1000 times in the length direction of the transparent conductor while keeping the sliding plate and the support member in parallel. Thereafter, it was visually confirmed whether cracks or the like occurred in each layer of the transparent conductor. The flexibility was evaluated as follows.
○: No crack was generated in a 30 mm × 30 mm region including the bent portion. Δ: One to 50 cracks were generated in the 30 mm × 30 mm region including the bent portion. X: The bent portion was included. Over 50 cracks occurred in a 30mm x 30mm area

(Measurement of light transmittance, reflectance and absorptance)
The transparent conductor surfaces of Examples 1 to 5, 7 to 17, 22, and 30 to 34 were measured for light transmittance, reflectance, and absorptance as follows.
Matching oil (refractive index = 1.515 manufactured by Nikon Corporation) was applied on the second high refractive index layer of the transparent conductor obtained in each example. Then, the 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 | permeability and reflectance of the transparent conductor were measured from the alkali free glass substrate side. At this time, measurement light (for example, light having a wavelength of 450 nm to 800 nm) is incident on the conduction region from an angle inclined by 5 ° with respect to the normal line of the surface of the alkali-free glass substrate. The light transmittance and reflectance were measured at U4100. The absorptance was calculated from a formula of 100− (transmittance + reflectance).

The value obtained by subtracting the reflection at the interface between the alkali-free glass substrate and the atmosphere (4%) and the reflection at the interface between the transparent substrate and the atmosphere (4%) from the measured value of the reflectance The reflectance of the transparent conductor was used. Also, the transmittance was added to the measured value of transmittance by 8% in consideration of the reflection at the interface between the alkali-free glass substrate and the atmosphere and the reflection of the transparent conductor at the interface between the transparent substrate and the atmosphere. The value was the transmittance of the transparent conductor.

On the other hand, the transparent conductors of Examples 6, 18 to 21, 23 to 29, and Comparative Examples 1, 3, and 7 were used in contact with air. Therefore, measurement light (for example, light having a wavelength of 450 nm to 800 nm) is incident on the conductive region without bonding an alkali-free glass substrate on the transparent conductor, and light is emitted by Hitachi, Ltd .: spectrophotometer U4100. The transmittance and reflectance were measured. The absorptance was calculated from a formula of 100− (transmittance + reflectance). The measurement light was incident from the second high refractive index layer side.

The value obtained by subtracting the reflection (4%) at the interface between the transparent substrate of the transparent conductor and the atmosphere from the measured value of the reflectance was taken as the reflectance of the transparent conductor. Also, the transmittance of the transparent conductor was determined by adding 4% to the measured value of the transmittance in consideration of the reflection of the transparent conductor at the interface between the transparent substrate and the atmosphere.

(Measuring method of luminous reflectance)
The luminous reflectance of each transparent conductor was measured with a spectrophotometer (U4100; manufactured by Hitachi High-Technologies Corporation). ΔR in the table represents the absolute value of the difference between the luminous efficiency of the conductive area and the luminous efficiency of the insulating area.

(Measurement method of a * value and b * value of conduction region)
The a * value and b * value in the L * a * b * color system of each transparent conductor were measured with a spectrophotometer U4100 manufactured by Hitachi, Ltd. For Examples 1 to 17 and 30 to 34, the a * value and b * value of the conduction region were measured, respectively.

(Measurement method of surface electrical resistance of conduction region)
Loresta EP MCP-T360 manufactured by Mitsubishi Chemical Analytech was brought into contact with the conduction region of each transparent conductor, and the surface electrical resistance of the conduction region was measured.

(Optical admittance)
The optical admittance of the transparent conductor obtained by the Example and the comparative example was specified. The optical admittance of wavelength 570nm of the first high refractive index layer side of the surface of the transparent metal Y1 ₌ x ₁ + iy 1, the optical admittance of wavelength 570nm of the second high refractive index layer side of the surface of the transparent metal film Y2 = x _The values of (x ₁ , y ₁ ) and (x ₂ , y ₂ ) when ₂ + iy ₂ are shown in the table.
For the transparent conductor obtained by patterning the first high-refractive index layer, the transparent metal film, and the second high-refractive index layer, the equivalent admittance of light having a wavelength of 570 nm on the surface of the laminate (conduction region) including the transparent metal film Is expressed as Y _E = x _E + iy _E , and the equivalent admittance of light with a wavelength of 570 nm on the surface of the laminate (insulating region) that does not include the transparent metal film; that is, Y _sub = x _sub + iy _sub The values of (x _E , y _E ) and (x _sub , y _sub ) are respectively shown in the table. Furthermore, when the value of ((x _E −x _sub ) ² + (y _E ) ² ) ^{0.5 and} the refractive index of the member in contact with the surface on the second high refractive index layer side of the laminate is n _env | The values of ((x _sub -x _env ) / (x _sub + x _env )) ² -((x _E -x _env ) / (x _E + x _env )) ² | are shown in the table.

The optical admittance of the layer included in the transparent conductor is the thin film design software Essential Mac OS Ver. It calculated in 9.4.375. Note that the thickness d, refractive index n, and absorption coefficient k of each layer necessary for the calculation are as follows. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

As shown in Tables 1 to 3, even when the first high refractive index layer or the second high refractive index layer is an amorphous layer made of ZnS—SiO ₂ , when the transparent metal film is an Ag alloy, The average transmittance of light having a wavelength of 400 to 800 nm was 86.6% or more, and the average transmittance of light having a wavelength of 400 to 1000 nm was 80.7% or more (Examples 1 to 34).

On the other hand, as shown in Table 4, when the first high refractive index layer or the second high refractive index layer contains ZnS, and the transparent metal film is made of only Ag (Comparative Examples 1 and 7). The average transmittance of light having a wavelength of 400 to 800 nm was 84.2 or 86.8%, and the average transmittance of light having a wavelength of 400 to 1000 nm was 80% or less. It is presumed that the transparent metal film was sulfided by the sulfur component contained in the first high refractive index layer or the second high refractive index layer, and the light transmittance was lowered.

In Comparative Example 2 in which a transparent metal film was produced by vapor deposition, a continuous film was not obtained and electricity was not conducted. Further, although the film became a continuous film when the thickness was 12 nm (Comparative Example 1), the average reflectance of light having a wavelength of 400 to 1000 nm was less than 80%. It is inferred that the transmittance was not sufficiently increased because of the inherent reflection of metal.

On the other hand, in the case where the second high refractive index layer was made of IZO, ICO, ITO, or a-GIO, the transparent metal film was corroded (Comparative Examples 3 to 6).

Further, when ZnS is contained in the first high refractive index layer or the second high refractive index layer, the flexibility of the transparent conductor is enhanced when SiO ₂ is contained together with ZnS. In particular, when the first high refractive index layer or the second high refractive index layer contains 10% by volume or more of SiO ₂ , the flexibility of the transparent conductor was good.

This application claims priority based on Japanese Patent Application No. 2013-229256 filed on Nov. 5, 2013. The contents described in the application specification and the drawings are all incorporated herein.

The transparent conductor obtained by the present invention has a high light transmittance and a low surface electric resistance because the transparent metal film is not easily sulfided. Therefore, it is preferably used in various optoelectronic devices such as various types of displays, touch panels, mobile phones, electronic paper, various solar cells, various electroluminescence light control elements, and the like.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 1st high refractive index layer 3 Transparent metal film 4 2nd high refractive index layer 100 Transparent conductor

Claims

A transparent substrate;
A first high refractive index layer including a dielectric material or an oxide semiconductor material having a refractive index of light having a wavelength of 570 nm higher than that of light having a wavelength of 570 nm of the transparent substrate;
One or more metals selected from the group consisting of germanium, bismuth, platinum group, copper, gold, molybdenum, zinc, gallium, tin, indium, neodymium, titanium, aluminum, tungsten, manganese, iron, nickel, yttrium, and magnesium A transparent metal film made of an alloy with silver;
A second high-refractive-index layer comprising a dielectric material or an oxide semiconductor material having a refractive index of light having a wavelength of 570 nm higher than that of light having a wavelength of 570 nm of the transparent substrate
Is a transparent conductor laminated in this order,
A transparent conductor in which at least one of the first high refractive index layer and the second high refractive index layer is an amorphous layer containing ZnS and a metal oxide or metal fluoride.
The transparent conductor according to claim 1, wherein the metal oxide included in the amorphous layer is SiO 2 .
The transparent conductor according to claim 1, wherein the transparent metal film is a metal pattern patterned into a predetermined shape.