WO2015133007A1

WO2015133007A1 - Method for producing transparent conductor

Info

Publication number: WO2015133007A1
Application number: PCT/JP2014/079789
Authority: WO
Inventors: 節夫徳弘; 一成多田; 仁一粕谷; 健一郎平田
Original assignee: コニカミノルタ株式会社
Priority date: 2014-03-07
Filing date: 2014-11-11
Publication date: 2015-09-11
Also published as: JPWO2015133007A1

Abstract

The objective of the present invention is to provide a method for producing a transparent conductor, which suppresses a decrease of the light transmittance due to sulfurization of a transparent metal layer material. In a method for producing a transparent conductor (1) according to the present invention, a first high-refractive-index layer (3a), a transparent metal layer (5) and a second high-refractive-index layer (3b) are sequentially laminated on a transparent substrate (2) that is continuously conveyed, and a sulfurization prevention layer is laminated between the first high-refractive-index layer (3a) and the transparent metal layer (5) and/or between the second high-refractive-index layer (3b) and the transparent metal layer (5). This method for producing a transparent conductor (1) is characterized by having a plurality of film formation steps for forming thin film layers on the transparent substrate (2) by means of a plurality of evaporation sources, and is also characterized in that a target of at least one evaporation source is configured of at least two split targets that are formed of different materials.

Description

Method for producing transparent conductor

The present invention relates to a method for producing a transparent conductor. More specifically, the present invention relates to a method for manufacturing a transparent conductor that suppresses a decrease in light transmittance due to sulfidation of a transparent metal layer material.

In recent years, low resistance transparent conductive films have been required for various devices such as touch panel materials, liquid crystal displays, plasma displays, inorganic and organic electroluminescence (EL) displays, and solar cells.

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

On the other hand, a capacitive touch panel display device has been developed, and the surface electrical resistance of the transparent conductive film is further reduced, and specifically, a resistance value of 50Ω / □ or less is strongly demanded. However, the ITO film that has been widely used conventionally has a resistance value of only about 150Ω / □, which is insufficient for the above demand.
Against this background, development of next-generation transparent conductive films to replace ITO has been actively conducted.

In response to the above problem, for example, Japanese Patent Application Laid-Open No. 2011-138628, Japanese Patent Application Laid-Open No. 2011-171292, etc. disclose a method for manufacturing a conductive element to which a silver mesh is applied. However, in the method using these silver meshes, since the mesh diameter is about 20 μm, it can be visually recognized by human eyes, and it is difficult to apply to a touch panel display device or the like. In addition, silver nanowires that are commercially available from some manufacturers have a minute size that is invisible to the naked eye and expresses electrical conductivity in the film, but the sheet resistance is about 60Ω / □, The quality required for current touch panel display devices was insufficient.

In addition, attempts have been made to reduce the resistance by using zinc oxide or the like, but in such a method, the film thickness of the conductive film needs to be laminated to about 200 nm, and it was formed in the manufacturing process. When stress is applied to the conductive film, cracks and the like are likely to occur in the film, resulting in a decrease in yield and a problem in terms of production efficiency. Moreover, it is difficult to apply the conductive film having such characteristics to a flexible touch panel and a curved member that are expected to be put to practical use in the near future.

Based on the above problems, a method of applying a silver vapor-deposited film as a transparent conductive film has been actively studied (for example, see Patent Document 1). Further, in order to increase the light transmittance of the transparent conductor, a silver thin film is formed by sputtering, a metal film having a high refractive index (for example, niobium oxide (Nb ₂ O ₅ ), IZO (indium zinc oxide), ICO A transparent conductive film having a structure sandwiched between (indium cerium oxide) and a-GIO (a film of an amorphous oxide made of gallium, indium and oxygen) is also proposed (for example, Patent Documents 2 to 4, Non-Patent Documents (See Patent Document 1). Furthermore, a method of sandwiching a silver thin film with a zinc sulfide film has also been proposed (see, for example, Non-Patent Documents 2 and 3).

However, for example, in a transparent conductor produced by sputtering with a structure such as zinc sulfide / silver thin film / zinc sulfide, the moisture resistance of the transparent conductor is sufficiently high, but when forming a silver thin film layer or a zinc sulfide layer During the formation of silver, silver is easily sulfided to form silver sulfide. As a result, there are problems such as a decrease in light transmittance of the transparent conductor and an increase in unnecessary absorption due to sulfurization.

Therefore, it is conceivable to provide a sulfidation prevention layer made of a metal oxide or the like between the transparent metal layer and the zinc sulfide layer for the purpose of preventing sulfidation of silver which is a transparent metal layer material. However, in the film formation method using the conventional sputtering method, since the film formation distance between the transparent metal layer and the sulfidation prevention layer is long, the zinc sulfide layer is formed before the sulfidation prevention layer is formed on the transparent substrate. This sulfur component sulfides the silver of the transparent metal layer material, making it difficult to obtain a transparent conductor having sufficient light transmittance.

By the way, it is preferable to continuously form a transparent conductive film on a long substrate such as a film by a vacuum film forming method in order to efficiently form a film with high productivity. As a method for realizing such film formation, a so-called roll using a feed roll in which a long substrate is wound in a roll shape and a take-up roll in which a film-formed substrate is wound in a roll shape. A to-roll film forming method is known.
In the case of forming a multilayer film using this roll-to-roll method, there has also been proposed an apparatus in which a partition wall and a differential pressure chamber are provided so as not to affect the film formation in the adjacent film formation chambers (for example, patents). (Refer to Document 5.) In this apparatus, as described above, since the film forming distance between the transparent metal layer and the sulfidation preventing layer is long, it is sufficient to prevent silver sulfidation of the transparent metal layer material. Absent.

Further, in a large sputtering apparatus, the target is divided in order to prevent the target size from becoming large and cracking due to a difference in thermal expansion between the backing plate (support for fixing the target) and the target (metal material). Although the technology is known (for example, refer to Patent Document 6), no consideration has been given to film formation using, for example, a metal oxide as a split target material.

Special table 2011-508400 gazette JP 2006-184849 A JP 2002-015623 A JP 2008-226581 A JP 2011-042848 A JP 2008-050696 A

The present invention has been made in view of the above-mentioned problems and situations, and a solution to that problem is to provide a method for producing a transparent conductor that suppresses a decrease in light transmittance due to sulfidation of a transparent metal layer material.

In order to solve the above problems, the present inventor has a plurality of film forming steps for forming a thin film layer on a transparent substrate by a plurality of evaporation sources in the process of examining the cause of the above problems. It has been found that the reduction of the light transmittance due to the sulfidation of the transparent metal layer material can be suppressed by the method for producing a transparent conductor, which is a split target composed of different materials, of the targets possessed by the two evaporation sources.

That is, the above-mentioned problem according to the present invention is solved by the following means.

1. A first high-refractive index layer, a transparent metal layer, and a second high-refractive index layer are sequentially laminated on a transparent substrate that is continuously transported, and further, the first high-refractive index layer and the second high-refractive index layer. A method for producing a transparent conductor, in which an anti-sulfurization layer is laminated between at least one rate layer and the transparent metal layer,
A plurality of film forming steps for forming a thin film layer on the transparent substrate by a plurality of evaporation sources;
A method for producing a transparent conductor, wherein the target of at least one of the evaporation sources is composed of at least two divided targets made of different materials.

2. 2. The method of manufacturing a transparent conductor according to claim 1, wherein the at least two divided targets include a divided target that is a material of the anti-sulfurization layer and a divided target that is a material of the transparent metal layer. .

3. The method for producing a transparent conductor according to item 2, wherein the split target that is a material of the transparent metal layer is silver or an alloy containing silver.

4. 4. The transparent conductor according to claim 2 or 3, wherein the splitting target, which is a material of the antisulfurization layer, is Zn, a metal oxide containing Zn, or a metal oxide containing Ga. Method.

The above-mentioned means of the present invention can provide a method for producing a transparent conductor that suppresses a decrease in light transmittance due to sulfidation of a transparent metal layer material.

The expression mechanism / action mechanism of the effect of the present invention is not clear, but is presumed as follows.

When a transparent conductor is formed in a continuous film forming process, sulfur components contained in the formation atmosphere of at least one of the first high refractive index layer and the second high refractive index layer remain in the formation atmosphere of the transparent metal layer. To do. If the film formation distance between the anti-sulfurization layer and the transparent metal layer is long, the surface of the transparent metal layer comes into contact with the sulfur component in the forming atmosphere, and metal sulfide is generated on the surface of the transparent metal layer. When the remaining sulfur component is combined with the sputtered transparent metal layer material, a metal sulfide is generated.

On the other hand, in the present invention, the deposition distance between the sulfidation prevention layer and the transparent metal layer is reduced, that is, the target constituting the sulfidation prevention layer and the target constituting the transparent metal layer are used as one evaporation source. By providing a so-called divided target, it is considered that silver sulfidation can be prevented and a decrease in light transmittance can be suppressed.

Schematic sectional view showing an example of a layer structure of a transparent conductor according to the present invention Schematic sectional view showing an example of a layer structure of a transparent conductor according to the present invention Schematic sectional view showing an example of a layer structure of a transparent conductor according to the present invention Graph showing the deposition rate of each target with respect to the electric power supplied to the evaporation source Schematic diagram showing an example of transparent conductor manufacturing equipment Schematic diagram of split targets in transparent conductor manufacturing equipment Schematic diagram of split targets in transparent conductor manufacturing equipment Schematic diagram of split targets in transparent conductor manufacturing equipment Schematic diagram showing an example of transparent conductor manufacturing equipment Schematic diagram showing an example of transparent conductor manufacturing equipment Schematic diagram showing a conventional transparent conductor manufacturing device

In the method for producing a transparent conductor of the present invention, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer are sequentially laminated on a transparent substrate that is continuously conveyed, A method of manufacturing a transparent conductor in which a sulfidation prevention layer is laminated between at least one of a high refractive index layer and a second high refractive index layer and a transparent metal layer, and a plurality of evaporation sources on a transparent substrate, It has a plurality of film forming steps for forming a thin film layer, and the target of at least one evaporation source is composed of at least two divided targets made of different materials. This feature is a technical feature common to the inventions according to claims 1 to 4.

As an embodiment of the present invention, from the viewpoint of preventing sulfidation of a metal that is a transparent metal layer material, at least two division targets are a division target that is a material for an antisulfation layer and a division target that is a material for a transparent metal layer. Are preferably included.

Further, from the viewpoint of reducing the surface electrical resistance, it is preferable that the divided target that is the material of the transparent metal layer is silver or an alloy containing silver.

In addition, from the viewpoint of preventing the sulfidation of the metal that is the transparent metal layer material, it is preferable that the split target that is the material of the sulfidation prevention layer is a metal oxide containing Zn or Zn, or a metal oxide containing Ga.

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

≪Layer structure of transparent conductor≫
1A to 1C are schematic cross-sectional views showing an example of a layer structure of a transparent conductor according to the present invention.
As shown in FIG. 1A, a transparent conductor 1 according to the present invention is formed on a transparent substrate 2 from the transparent substrate 2 side, a first high refractive index layer 3a, an antisulfurization layer 4a (also referred to as a first antisulfurization layer). ), A transparent metal layer 5 and a second high refractive index layer 3b are sequentially laminated.
The first high refractive index layer 3a or the second high refractive index layer 3b contains at least zinc sulfide (ZnS).

In the transparent conductor 1 according to the present invention, as shown in FIG. 1B, an antisulfurization layer 3 b (also referred to as a second antisulfurization layer) is provided between the second high refractive index layer 3 b and the transparent metal layer 5. It is good also as a formed structure, and as shown to FIG. 1C, between the 1st high refractive index layer 3a and the transparent metal layer 5, the 1st antisulfurization layer 4a, the 2nd high refractive index layer 3b, and a transparent metal The second sulfidation preventing layer 4b may be formed between the layer 5 and the layer 5.

As described above, by providing the

antisulfurization layer

4a or 4b between at least the first high refractive index layer 3a or the second high refractive index layer 3b and the transparent metal layer 5, the first high refractive index layer 3a or the first high

refractive index layer

3a or 2 It is possible to prevent movement and mixing of sulfur atoms constituting the zinc sulfide contained in the high refractive index layer 3b to the transparent metal layer 5, which is a preferable mode.

That is, when the transparent metal layer 5 (for example, silver layer) and the first high refractive index layer 3a or the second high refractive index layer 3b containing at least a metal sulfide such as ZnS are formed adjacent to each other, the metal sulfide There is a problem that an object (for example, silver sulfide) is easily generated, and the light transmittance of the transparent conductor 1 is likely to be lowered.

In the transparent metal layer 5, the metal sulfide is presumed to be generated under the following conditions.

When the transparent metal layer 5 is formed on the first high refractive index layer 3a containing at least zinc sulfide, the unreacted sulfur component in the first high refractive index layer 3a containing zinc sulfide is converted into the transparent metal layer 5 The material (for example, silver) is repelled into the forming atmosphere. Then, the ejected sulfur component reacts with a metal, for example, silver, and metal sulfide (silver sulfide) is deposited on the first high refractive index layer 3a containing zinc sulfide.
Moreover, when forming the transparent metal layer 5 on the 1st high refractive index layer 3a containing zinc sulfide by the continuous film-forming process, it is contained in the formation atmosphere of the 1st high refractive index layer 3a containing zinc sulfide. The sulfur component remains in the atmosphere of the transparent metal layer 5. And this sulfur component and a metal react, and metal sulfide (silver sulfide) deposits on the 1st high refractive index layer 3a containing a zinc sulfide. Alternatively, there are some Zn and unbonded sulfur on the outermost surface of the first high refractive index layer 3a, and then when the transparent metal layer 5 is laminated, the unbonded active sulfur component becomes transparent metal. Bonds with constituent atoms of layer 5, for example silver.

On the other hand, when the second high refractive index layer 3b containing at least zinc sulfide is formed on the transparent metal layer 5, the metal in the transparent metal layer 5 is a material of the second high refractive index layer 3b containing zinc sulfide. Is played in the forming atmosphere. The ejected metal reacts with the sulfur component, and metal sulfide is deposited on the surface of the transparent metal layer 5. Furthermore, a metal sulfide is also generated on the surface of the transparent metal layer 5 when the surface of the transparent metal layer 5 comes into contact with the sulfur component in the forming atmosphere. Alternatively, when depositing the zinc sulfide constituting the second high refractive index layer 3b, the zinc and sulfur are partly present in the atmosphere in a free state, and the free sulfur is present in the transparent metal layer 5 Bonds to a constituent atom, such as silver.

On the other hand, in the transparent conductor 1 according to the present invention, for example, as shown in FIG. 1A, an antisulfurization layer 4a is formed on the first high refractive index layer 3a. By adopting such a configuration, the first high refractive index layer 3a is protected by the sulfidation preventing layer 4a, so that the sulfur component in the first high refractive index layer 3a is not easily ejected when the transparent metal layer 5 is formed. Even if the first high refractive index layer 3a and the transparent metal layer 5 are continuously formed, the sulfur component contained in the atmosphere in which the first high refractive index layer 3a is formed reacts with the constituent components of the sulfurization preventing layer 4a. Alternatively, by being adsorbed by the constituent components of the sulfidation prevention layer 4a, the atmosphere in which the transparent metal layer 5 is formed is less likely to contain sulfur, and the formation of metal sulfide is suppressed.

Further, in the transparent conductor 1 according to the present invention, as shown in FIG. 1B, the sulfidation preventing layer 4b is laminated on the transparent metal layer 5. In such a configuration, since the transparent metal layer 5 is protected by the antisulfurization layer 4b, the metal in the transparent metal layer 5 is not easily ejected when the second high refractive index layer 3b is formed. Further, the sulfur component in the atmosphere in which the second high refractive index layer 3 b is formed is less likely to come into contact with the surface of the transparent metal layer 5. As a result, metal sulfides are hardly generated on the surface of the transparent metal layer 5.

In addition to the transparent substrate 2, the high refractive index layers 3a and 3b, the antisulfurization layers 4a and 4b, and the transparent metal layer 5, the transparent conductor 1 according to the present invention includes a known functional layer as necessary. It may be provided. For example, an underlayer that can be a growth nucleus when the transparent metal layer 5 is formed may be formed between the transparent metal layer 5 and the first high refractive index layer 3a.

≪Method for producing transparent conductor≫
In the method for producing a transparent conductor of the present invention, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer are sequentially laminated on a transparent substrate that is continuously conveyed, A method of manufacturing a transparent conductor in which a sulfidation prevention layer is laminated between at least one of a high refractive index layer and a second high refractive index layer and a transparent metal layer, and a plurality of evaporation sources on a transparent substrate, It has a plurality of film forming steps for forming a thin film layer, and the target of at least one evaporation source is composed of at least two divided targets made of different materials.
Here, the “divided target” means each target obtained by dividing one target into at least two parts having different chemical compositions (see FIGS. 4A to 4C).

As a method for forming the high refractive index layer, the sulfurization preventing layer and the transparent metal layer, a sputtering method may be mentioned. The type of the sputtering method is not particularly limited, and ion beam sputtering, magnetron sputtering, reactive sputtering, bipolar sputtering, bias sputtering, RF sputtering, counter sputtering, and the like can be used. Among these, the transparent metal layer is preferably a layer formed by an RF sputtering method or a counter sputtering method, and more preferably a layer formed by a counter sputtering method. When the transparent metal layer is a layer formed by an RF sputtering method or a counter sputtering method, the transparent metal layer becomes dense and surface smoothness is likely to increase. As a result, the surface electrical resistance of the transparent metal layer can be further reduced, and the light transmittance can be improved.

Further, in the present invention, it is preferable that at least two split targets include a split target that is a material for an antisulfurization layer and a split target that is a material for a transparent metal layer. Thereby, the film-forming distance between the transparent metal layer and the sulfidation prevention layer is reduced, and sulfidation of the transparent metal layer material due to the sulfur component can be prevented.

In addition, in order to form the sulfidation prevention layer as an extremely thin film, it is necessary to reduce the input power to the metal oxide target and slow down the sputtering rate. The film cannot be formed. In the present invention, the sulfide prevention layer material (for example, metal oxide) target is a divided target that is disposed adjacent to the metal (for example, silver) target, so that the input power to the evaporation source is not reduced. Since the same effect as reducing the input power to the metal oxide target can be obtained, the antisulfurization layer can be stably formed.

By the way, when the input power to the target and the film forming speed just above the target are plotted on the graph in a state where the transparent substrate is not transported, the relationship shown in FIG. 2 is obtained.

As shown by the curve A in FIG. 2, silver could be deposited at high speed even when the input power was small. On the other hand, as shown by the curve B in FIG. 2, ZnS—SiO _{2 which} is also a high refractive index layer material can only obtain a film formation rate of about 1/5 of silver. As the input power to ZnS—SiO ₂ is increased, the film formation rate can be increased. However, when the input power is 13 W / cm ² or more, the discharge becomes unstable and the film formation cannot be continued. . Therefore, in order to deposit ZnS—SiO ₂ stably at a high speed, it is preferable to apply a power of about 10 W / cm ² . The same applies to ZnS indicated by curve C in FIG.
In the present invention, since the transparent metal layer material and the antisulfurization layer material, which are ultrathin films, are provided as a split target on one evaporation source, the number of targets of the high refractive index layer can be increased. Therefore, even if the conveyance speed is increased, a high refractive index layer having a sufficient layer thickness can be formed with an input power of 10 W / cm ² .

In addition, it is possible to form a film while maintaining the film formation speed of Ag by increasing the length of the target of the high refractive index layer, and more specifically, by arranging a plurality of targets. This is not preferable because the equipment cost becomes high.

In addition, as shown by the curve D in FIG. 2, the metal oxide target (ITO, IZO, GZO, ZnO, IGZO), which is an antisulfurization layer material, is stable at an input power of 4 W / cm ² or more. Sputtering failed. However, in the present invention, since the anti-sulfurization layer material target is a split target, the same effect as reducing the input power to the split target can be obtained, and stable sputtering can be achieved.

Hereinafter, a manufacturing apparatus suitably used in the method for manufacturing a transparent conductor of the present invention will be described, and then a method for manufacturing a transparent conductor using the manufacturing apparatus will be described.

≪Transparent conductor manufacturing apparatus and manufacturing method using the same >>
Hereinafter, the manufacturing apparatus which manufactures the transparent conductor 1 which concerns on this invention, and the manufacturing method using the same are demonstrated.
In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and duplicate descriptions are omitted.

<Manufacturing equipment>
FIG. 3 is a schematic view showing an example of a transparent conductor manufacturing apparatus according to the present invention.
As shown in FIG. 3, the manufacturing apparatus 100 mainly includes a feed roller 180 that sends out the transparent substrate 2 before forming various functional layers into the vacuum chamber 110, guide

rollers

181 and 183 that guide the transparent substrate 2, and a transparent substrate. 2, a main roller 182 that transports 2, a winding roller 184 that winds up the transparent substrate 2 on which various functional layers are formed, an evaporation source 131 that forms a first high refractive index layer, an evaporation that forms a sulfidation prevention layer and a transparent metal layer. It comprises a source 151, an evaporation source 171 that forms the second high refractive index layer, and partition walls 190 to 195 that partition the space in the vacuum chamber 110.

The inside of the vacuum chamber 110 is partitioned by a main roller 182 and partition walls 190 to 195. Around the main roller 182, there are an unwind chamber 120, a first film formation chamber 130, a first differential pressure chamber 140, a second formation chamber. A film chamber 150, a second differential pressure chamber 160, and a third film formation chamber 170 are formed.

The unwinding chamber 120 includes an inner wall surface of the vacuum chamber 110, a peripheral surface of the main roller 182 and

partition walls

190 and 195 extending from the inner wall surface of the vacuum chamber 110 to the vicinity of the peripheral surface of the main roller 182. Yes.
Here, the ends of the

partition walls

190 and 195 extend to a position where they do not contact the transparent substrate 2 stretched around the main roller 182, close to the peripheral surface of the main roller 182, and the unwind chamber 120 and the first The film formation chamber 130 and the third film formation chamber 170 are separated in a substantially airtight manner.
The other partition walls 191 to 194 are similarly configured, and the first film formation chamber 130 and the first differential pressure chamber 140 are partitioned by the partition wall 191, and the first differential pressure chamber 140 and the second film formation chamber 150 are formed by the partition wall 192. The second film forming chamber 150 and the second differential pressure chamber 160 are partitioned by a partition wall 193, and the second differential pressure chamber 160 and the third film forming chamber 170 are partitioned by a partition wall 194. Since each chamber is partitioned by the partition walls 190 to 195, it is possible to suppress the target of each film formation chamber from entering another film formation chamber. In particular, for example, the sulfur component contained in the material of the first high refractive index layer or the second high refractive index layer is prevented from entering the second film forming chamber 150, and corrosion of the transparent metal layer containing silver is prevented. Can be suppressed.

The unwinding chamber 120, the first film forming chamber 130, the first differential pressure chamber 140, the second film forming chamber 150, the second differential pressure chamber 160, and the third film forming chamber 170 are respectively evacuated (not shown). And an inert gas supply means (not shown) and the like are provided, and the degree of vacuum in each chamber can be adjusted.
The vacuum exhaust means is not particularly limited. For example, a vacuum pump such as a turbo pump, a mechanical booster pump, a rotary pump, or a dry pump, an auxiliary means such as a cryocoil, an ultimate vacuum degree or exhaust amount adjusting means, etc. A known (vacuum) evacuation means or the like used in a vacuum film forming apparatus can be used.

As described above, the partition walls 190 to 195 are provided between the chambers and are separated from each other in a substantially hermetic manner. However, since the transparent substrate 2 transported through the chambers passes, a completely hermetic state cannot be formed. Therefore, the first differential pressure chamber 140 is provided between the first film formation chamber 130 and the second film formation chamber 150, and the second differential pressure chamber 160 is provided between the second film formation chamber 150 and the third film formation chamber 170. By providing and adjusting the degree of vacuum of the first differential pressure chamber 140 and the second differential pressure chamber 160, the target of each film formation chamber is prevented from entering another film formation chamber.
Specifically, the degree of vacuum in the first differential pressure chamber 140 and the second differential pressure chamber 160 is lower than that in the first to third

film formation chambers

130, 150, and 170, that is, the pressure is high. By doing so, it is possible to suppress the target in each film formation chamber from entering another film formation chamber.
In particular, for example, the sulfur component contained in the first high-refractive index layer or the second high-refractive index layer is prevented from entering the second film forming chamber 150 and the corrosion of the transparent metal layer containing silver is suppressed. Can do.

Further, from the viewpoint of suppressing the corrosion of the transparent metal layer, the degree of vacuum of the second film formation chamber 150 is lower than that of the first film formation chamber 130 and the third film formation chamber 170, that is, the pressure is high. It is preferable that Thereby, it can suppress that the sulfur component in the 1st film-forming chamber 130 and the 3rd film-forming chamber 170 penetrate | invades into the 2nd film-forming chamber 150, and can suppress corrosion of the transparent metal layer containing silver.

The transparent substrate 2 used in the manufacturing apparatus 100 is formed in a long length, is unwound from the feed roller 180 in the unwind chamber 120, and is taken up by the take-up roller 184. The transparent substrate 2 unwound from the delivery roller 180 is conveyed to the main roller 182 via the guide roller 181, and sequentially in the first film formation chamber 130, the second film formation chamber 150, and the third film formation chamber 170. A thin film layer is formed, and is further wound around a winding roller 184 via a guide roller 183.

Here, when moisture is generated from the transparent substrate 2 by performing vacuum evacuation, heat treatment, or the like, the composition of each layer formed by sputtering changes, so the moisture is removed from the transparent substrate 2 before forming the layer. It is preferable. Specifically, it is preferable to perform preliminary heating, evacuation by a cryopump, or the like on the transparent substrate 2, and the manufacturing apparatus 100 may have a configuration for performing them.

Further, in order to improve the adhesion between the transparent substrate 2 and a layer formed adjacent to the transparent substrate 2, it is preferable to perform a surface cleaning process on the transparent substrate 2 before forming the layer. Specifically, it is preferable to perform an ion bombardment process, a plasma process, etc. with respect to the transparent substrate 2, and the manufacturing apparatus 100 may be equipped with the structure for performing them.

The feed roller 180 supplies the long transparent substrate 2 and sends it to the downstream side in the transport direction X. Further, the winding roller 184 winds the layer-formed transparent substrate 2. The feed roller 180 and the take-up roller 184 are provided in the unwind chamber 120.
The control unit (not shown) of the manufacturing apparatus 100 synchronizes the feeding of the transparent substrate 2 by the feeding roller 180 and the winding of the transparent substrate 2 on which the layer has been formed by the winding roller 184, so Layers are sequentially formed in the first film formation chamber 130, the second film formation chamber 150, and the third film formation chamber 170 while the transparent substrate 2 is conveyed in the longitudinal direction along a predetermined conveyance path. Therefore, the unwinding chamber 120 is the most upstream chamber in the transport direction X of the transparent substrate 2 and the most downstream chamber in the manufacturing apparatus 100.

The

guide rollers

181 and 183 are normal guide rollers that are provided in the unwind chamber 120 and guide the transparent substrate 2 along a predetermined transport path.

The main roller 182 is a cylindrical member that rotates in the direction of the arrow in FIG.
The main roller 182 wraps the transparent substrate 2 conveyed by the guide roller 181 in a predetermined path around a predetermined area of the peripheral surface and conveys the transparent substrate 2 in the longitudinal direction while holding it at a predetermined position. The transparent substrate 2 is passed through the first differential pressure chamber 140, the second film formation chamber 150, the second differential pressure chamber 160, and the third film formation chamber 170 in this order, and is sent to the guide roller 183 in the unwind chamber 120.

The main roller 182 also functions as a counter electrode for the evaporation source 131 of the first film formation chamber 130, the evaporation source 151 of the second film formation chamber 150, and the evaporation source 171 of the third film formation chamber 170.

Further, the main roller 182 may incorporate a cooling means for cooling the transparent substrate 2. The cooling means for the main roller 182 is not particularly limited, and may be a cooling means for circulating a refrigerant or the like, or a cooling means using a piezo element or the like. The cooling means is configured to cool the temperature of the transparent substrate 2 to about −20 to 65 ° C., for example.

The evaporation source 131 is provided in the first film forming chamber 130, and a target 133 that is a raw material for the first high refractive index layer is attached to the sputtering cathode 132. The evaporation source 131 forms a first high refractive index layer having a layer thickness corresponding to the input power amount on the transparent substrate 2 conveyed by the main roller 182 when power is input.

The evaporation source 151 is provided in the second film formation chamber 150, and the split targets 153 a and 153 b that are raw materials for the sulfurization prevention layer and the transparent metal layer are attached to the sputtering cathode 152. Specifically, as shown in FIG. 4A, the split target 153a of the sulfidation prevention layer (first sulfidation prevention layer) is upstream in the transport direction X upstream of the transparent substrate 2, and the transparent metal is downstream in the transport direction X of the transparent substrate 2. A layer split target 153b is provided. As shown in FIG. 4B, the split target provided on the sputtering cathode 152 is provided with a transparent metal layer split target 153 b on the upstream side in the transport direction X of the transparent substrate 2, and prevents sulfurization on the downstream side in the transport direction X of the transparent substrate 2. A split target 153c for the layer (second anti-sulfur layer) may be provided, and as shown in FIG. 4C, the first anti-sulfur layer is divided from the upstream side toward the downstream side in the transport direction X of the transparent substrate 2. You may provide the target 153a, the division | segmentation target 153b of a transparent metal layer, and the division | segmentation target 153c of a 2nd sulfurization prevention layer.
The evaporation source 151 forms an anti-sulfurization layer and a transparent metal layer having a layer thickness corresponding to the input power amount on the transparent substrate 2 conveyed by the main roller 182 when power is input.

Further, in the second film forming chamber 150, as shown in FIG. 5, a partition plate 196 may be provided on the extended line of the boundary between the divided

targets

153a and 153b so that the divided targets are not mixed. The partition plate 196 is held by a holding shaft 197 extending substantially horizontally between the opposing wall surfaces of the

partition walls

192 and 193.
Both ends of the partition plate 196 are disposed so as not to contact the main roller 182 and the divided

targets

153a and 153b, but may be provided to extend as close as possible so that the divided targets do not mix. preferable.
The partition plate 196 may be provided in a straight line with respect to the direction perpendicular to the divided target surface, or may be provided in a curved shape in one of the divided

targets

153a and 153b.
Note that the partition plate 196 is appropriately provided on the extended line of the boundary according to the number of division targets (see FIGS. 4A to 4C).

In the second film forming chamber 150, an opening limiting mask (not shown) may be provided between the transparent substrate 2 transported to the main roller 182 and the evaporation source 151. The opening limiting mask is not provided in the first film formation chamber 130 and the third film formation chamber 170. By providing the aperture limiting mask, the width of the region of the evaporation source 151 facing the transparent substrate 2 in the substrate transport direction can be substantially reduced. The distance between the opening limiting mask and the transparent substrate 2 is preferably within 5 mm.

In general, a thin layer is formed by reducing the amount of input power input to the evaporation source. However, when the transparent metal layer is formed by reducing the amount of electric power input to the evaporation source, the average light absorptance of the formed transparent metal layer increases and the average light transmittance decreases.
On the other hand, when forming a thin transparent metal layer using a material containing silver, by using an aperture limiting mask, the width in the substrate transport direction of the region facing the transparent substrate 2 in the divided target 153b can be increased. A transparent metal layer having a thin layer thickness can be formed without reducing the function.
Although it is conceivable to reduce the width of the region facing the transparent substrate 2 in the substrate transport direction by reducing the width of the evaporation source 151 itself in the substrate transport direction, an existing apparatus configuration or target may be used. Since it becomes impossible, cost increases and it is not preferable.

The evaporation source 171 is provided in the third film formation chamber 170, and a target 173, which is a raw material for the second high refractive index layer, is attached to the sputtering cathode 172. The evaporation source 171 forms a second high refractive index layer having a layer thickness corresponding to the input power amount on the transparent substrate 2 conveyed by the main roller 182 when power is input.

As the sputtering

cathodes

132, 152, and 172, those of the so-called magnetron cathode type in which a magnet is disposed inside and the plasma is confined by a magnetic field to increase the sputtering efficiency are preferable. As

such sputtering cathodes

132, 152 and 172, either a flat cathode or a rotary cathode may be used. However, since the use efficiency of the target is high and the layer thickness distribution of the formed layer can be easily obtained, the rotary cathode is used. More preferably.
The magnetic flux density of the magnet is preferably in the range of 300 to 1000 G (3 × 10 ⁻² to 10 × 10 ⁻² T).

Examples of sputtering conditions in each of the

film forming chambers

130, 150, and 170 include an inert gas flow rate of 5 to 40 sccm (Standard Cubic Centimeter per Minute), a pressure of 0.1 to 1.0 Pa, such as Ar, Kr, and Xe. And by setting to such conditions, it can suppress that the surface of each layer formed becomes rough. The layer thickness of each layer formed in each of the

film formation chambers

130, 150, and 170 is preferably monitored by a layer thickness monitor such as a crystal resonator or an interferometer.

In the manufacturing apparatus 100 described above, the first differential pressure chamber 140 is provided between the first film formation chamber 130 and the second film formation chamber 150, and the second film formation chamber 150, the third film formation chamber 170, However, the first differential pressure chamber 140 and the second differential pressure chamber 160 may not be provided.

In the manufacturing apparatus 100 described above, the first film formation chamber 130, the second film formation chamber 150, and the third film formation chamber 170 are provided. However, the first differential pressure chamber 140 and the second differential pressure are provided. Instead of the chamber 160, a film forming chamber for forming another functional layer constituting the transparent conductor may be provided.
That is, as shown in FIG. 6, the manufacturing apparatus 200 includes a first film formation chamber 230 and a second film formation chamber 240 that form the first high refractive index layer, a third formation layer that forms the sulfidation prevention layer and the transparent metal layer. The film chamber 250 and the fourth film forming chamber 260 and the fifth film forming chamber 270 for forming the second high refractive index layer may be provided.

<How to use manufacturing equipment>
The transparent conductor according to the present invention is preferably performed using the manufacturing apparatus 100. Hereinafter, the case where the said manufacturing apparatus 100 is used is demonstrated.

First, a film forming process of the first high refractive index layer is performed by the evaporation source 131 on the transparent substrate 2 that is fed from the feed roller 180 and conveyed by the main roller 182.
Subsequently, a film forming step of an antisulfurization layer and a transparent metal layer is performed on the transparent substrate 2 conveyed by the main roller 182 by the evaporation source 151. Under the present circumstances, you may perform the film-forming process of a sulfide prevention layer and a transparent metal layer through the opening restriction | limiting mask which restrict | limits the width | variety in the board | substrate conveyance direction X of the area | region facing the transparent substrate 2. FIG. By forming the sulfidation prevention layer and the transparent metal layer through the opening limiting mask, the sulfidation prevention layer and the transparent metal layer having a thinner thickness than the first and second high refractive index layers can be formed without reducing the function. Can be formed.
Subsequently, a film forming process of the second high refractive index layer is performed by the evaporation source 171 on the transparent substrate 2 conveyed by the main roller 182.
Thus, the transparent substrate 2 on which the first high refractive index layer, the sulfidation preventing layer, the transparent metal layer, and the second high refractive index layer are formed is wound up by the winding roller 184.
As described above, a desired transparent conductor can be manufactured.

≪Details of layer structure of transparent conductor≫
Hereinafter, the details of each layer and the material constituting the transparent conductor 1 according to the present invention will be described.

<Transparent substrate>
The transparent substrate 2 may be a transparent substrate and may be the same as the transparent substrate of various conventionally known display devices.
Here, in the present invention, transparent means that the light transmittance at a wavelength of 550 nm is 50% or more.

As the transparent substrate 2, for example, a glass substrate, a cellulose ester resin (for example, triacetyl cellulose, diacetyl cellulose, acetyl propionyl cellulose, etc.), a polycarbonate resin (for example, Panlite, Multilon (both manufactured by Teijin Ltd.)), cyclo Olefin resins (for example, ZEONOR (manufactured by ZEON CORPORATION), ARTON (manufactured by JSR), APPEL (manufactured by Mitsui Chemicals)), acrylic resins (for example, polymethyl methacrylate, acrylite (manufactured by Mitsubishi Rayon), Sumipex (Sumitomo) Chemical)), polyimide, phenol resin, epoxy resin, polyphenylene ether (PPE) resin, polyester resin (eg, polyethylene terephthalate (PET), polyethylene naphthalate (PEN)), polyethersulfone, ABS AS resin, MBS resin, polystyrene, methacrylic resins, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resins), such as a transparent resin film comprising a styrene block copolymer resins. When the transparent substrate 2 is a transparent resin film, the transparent resin film may contain two or more kinds of resins.

From the viewpoint of transparency, examples of the material of the transparent substrate 2 include a glass substrate, cellulose ester resin, polycarbonate resin, polyester resin (particularly polyethylene terephthalate), triacetyl cellulose, cycloolefin resin, phenol resin, epoxy resin, and polyphenylene. A transparent resin film made of ether (PPE) resin, polyethersulfone, ABS / AS resin, MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin), styrene block copolymer resin, or the like is preferable. .

The transparent substrate 2 preferably has high transparency to visible light, and the average transmittance of light having a wavelength of 450 to 800 nm is preferably 70% or more, more preferably 80% or more, and still more preferably 85% or more. is there. When the average light transmittance of the transparent substrate 2 is 70% or more, the light transmittance of the transparent conductor 1 is likely to increase. The average absorption rate of light at a wavelength of 450 to 800 nm of the transparent substrate 2 is preferably 10% or less, more preferably 5% or less, and still more preferably 3% or less.
Here, 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 2. On the other hand, the average absorptance is measured by measuring the average reflectance of the transparent substrate 2 by making light incident from the same angle as that of the average transmittance, and obtaining “average absorptance = 100− (average transmittance + average reflectance)”. calculate. The average transmittance and average reflectance are measured with a spectrophotometer.

The refractive index of light at a wavelength of 570 nm of the transparent substrate 2 is preferably 1.40 to 1.95 at 25 ° C., more preferably 1.45 to 1.75, still more preferably 1.45 to 1. .70. The refractive index of the transparent substrate 2 is usually determined by the material of the transparent substrate 2. The refractive index of the transparent substrate 2 is measured with an ellipsometer.

The haze value of the transparent substrate 2 is preferably in the range of 0.01 to 2.5, more preferably in the range of 0.1 to 1.2. The haze value of the transparent conductor 1 is suppressed as the haze value of the transparent substrate 2 is 2.5 or less. The haze value is measured with a haze meter.

The thickness of the transparent substrate 2 is preferably in the range of 1 μm to 20 mm, more preferably in the range of 10 μm to 2 mm. When the thickness of the transparent substrate 2 is 1 μm or more, the strength of the transparent substrate 2 is increased, and it is possible to suppress cracking or tearing when the first high refractive index layer 3a is formed. On the other hand, if the thickness of the transparent substrate 2 is 20 mm or less, the flexibility of the transparent conductor 1 is sufficient. Furthermore, the thickness of the apparatus using the transparent conductor 1 can be reduced. Moreover, the apparatus using the transparent conductor 1 can also be reduced in weight.

As described above, a glass substrate, a resin film, or the like is used as the transparent substrate 2. On the surface, for example, a smooth layer (clear hard coat layer: CHC layer), a protective layer, an adhesion layer, a reflective layer is used. Further, a layer (film) for expressing various functions such as an antireflection layer may be formed. When the smooth layer is formed, the average surface roughness Ra is preferably 3 nm or less.

<First high refractive index layer>
The first high refractive index layer 3 a is a layer that adjusts the light transmittance (optical admittance) of the transparent metal layer 5.

The first high refractive index layer 3a includes a dielectric material or an oxide semiconductor material having a refractive index higher than the refractive index of the transparent substrate 2 described above.
The dielectric material or the oxide semiconductor material included in the first high refractive index layer 3a may be an insulating material or a conductive material. A metal oxide can be used as the dielectric material or the oxide semiconductor material. Examples of metal _oxides, TiO _2, ITO (indium tin _{_{_{_{oxide), 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 ( indium zinc oxide), AZO (aluminum oxide zinc), GZO (gallium oxide, zinc), ATO (antimony tin oxide), ICO (indium cerium oxide), Bi ₂ Examples include O ₃ , Ga ₂ O ₃ , GeO ₂ , WO ₃ , HfO ₂ , a-GIO (amorphous oxide composed of gallium, indium, and oxygen). The first high refractive index layer 3a may contain only one kind of the metal oxide or two or more kinds.

Further, as described above, zinc sulfide can be used as the dielectric material or the oxide semiconductor material included in the first high refractive index layer 3a. When zinc sulfide is contained in the first high refractive index layer 3 a, moisture permeation to the transparent metal layer 5 can be suppressed and corrosion of the transparent metal layer 5 can be suppressed. The first high refractive index layer 3a may contain only zinc sulfide, or may contain other materials together with zinc sulfide. Material contained together with zinc sulphide, a metal oxide or SiO ₂ or the like which can be used as the dielectric material or an oxide semiconductor material, as will be described later, particularly preferably SiO _2. When SiO ₂ is contained together with zinc sulfide, the first high refractive index layer 3a is likely to be amorphous, and the flexibility of the transparent conductor 1 is likely to be enhanced.

When the first high refractive index layer 3a contains other materials together with zinc sulfide, the content of zinc sulfide is 0. 0 relative to the total number of moles of all the materials constituting the first high refractive index layer 3a. It is preferably in the range of 1 to 95% by mass, more preferably in the range of 50 to 90% by mass, and still more preferably in the range of 60 to 85% by mass. When the content of zinc sulfide is large, the sputtering rate is increased and the formation rate of the first high refractive index layer 3a is increased. On the other hand, when many components other than zinc sulfide are contained, the amorphousness of the first high refractive index layer 3a is increased, and cracking of the first high refractive index layer 3a is suppressed.

The refractive index of light at 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 at a wavelength of 570 nm of the transparent substrate 2, and is preferably 0.4 to 1.0. Larger is more preferable.
On the other hand, the specific refractive index of light at a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the first high refractive index layer 3a is preferably greater than 1.5 at 25 ° C. More preferably, it is within the range of .5, and even more preferably within the range of 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 transparent conductor 1 is sufficiently adjusted by the first high refractive index layer 3a. The refractive index of the first high refractive index layer 3a is adjusted by the refractive index of the material included in the first high refractive index layer 3a and the density of the material included in the first high refractive index layer 3a.

The layer thickness of the first high refractive index layer 3a is preferably in the range of 15 to 150 nm, more preferably in the range of 20 to 80 nm. When the thickness of the first high refractive index layer 3a is 15 nm or more, the optical admittance of the transparent conductor 1 is sufficiently adjusted by the first high refractive index layer 3a. On the other hand, if the thickness of the first high refractive index layer 3a is 150 nm or less, the light transmittance of the region where the first high refractive index layer 3a is formed is unlikely to decrease. The layer thickness of the first high refractive index layer 3a is measured with an ellipsometer.

(Amorphized metal material)
The first high refractive index layer 3a preferably contains zinc sulfide, but more preferably contains amorphous zinc sulfide. Since the amorphous zinc sulfide is contained in the first high refractive index layer 3a, the stress generated in the transparent conductor 1 can be reduced, and the occurrence of warpage in the transparent conductor 1 can be suppressed. It is possible to suppress the generation of cracks when the transparent conductor 1 is bent. Furthermore, the light transmittance of the first high refractive index layer 3a can be improved by containing amorphous zinc sulfide in the first high refractive index layer 3a.

By making the first high refractive index layer 3a contain an amorphous metal material together with zinc sulfide, the zinc sulfide can be made amorphous. The content of the amorphized metal material can be appropriately changed, whereby the refractive index of light can be changed. Therefore, the light transmittance can be made desired. Specifically, the first high refractive index layer 3a is not amorphized by containing, for example, TiO ₂ or Nb ₂ O ₅ which is a transparent material having a higher refractive index than zinc sulfide as an amorphized metal material. That is, the reflection band can be expanded as compared with the first high refractive index layer made of crystalline zinc sulfide alone. Thereby, adjustment of the optical characteristic of the transparent conductor 1 becomes easy.

In addition, zinc sulfide that has been amorphized using an amorphized metal material has better durability. Therefore, the transparent metal layer 5 can be protected more reliably. Therefore, for example, by containing Si ₃ N ₄ or Al ₂ O ₃ as an amorphized metal material together with zinc sulfide in the first high refractive index layer 3a, it is possible to improve the scratch resistance of the transparent conductor 1. Become.

As the amorphized metal material, for example, a metal oxide, a metal fluoride, a metal nitride, or the like can be used.

Examples of the metal oxide used as the amorphized metal material include TiO ₂ , In ₂ O ₅ , 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 , ITO (InSnO), IGZO (InGaZnO), IZO (InZnO), AZO (AlZnO), GZO (GaZnO), ATO (AlSnO), ICO ( InCeO), Bi ₂ O ₃ , a-GIO (GaInO), Ga ₂ O ₃ , GeO ₂ , SiO ₂ , Al ₂ O ₃ , HfO ₂ , SiO, MgO, Y ₂ O ₃ , WO _{3 and the} like.
In the present invention, the metal oxide is used to include SiO ₂ .

Among these, SiO ₂ and TiO ₂ are preferable. When SiO ₂ is used, zinc sulfide can be made amorphous even if its content is small. Therefore, by incorporating the SiO _2, after amorphization of zinc sulfide, high adhesion (peeling resistance) and high durability (e.g., moisture resistance, etc.) it can be particularly well achieved a. In addition, since TiO ₂ exhibits a particularly high refractive index among transparent materials, by using TiO ₂ , a wide reflection band can be obtained and the optical characteristics of the transparent conductor 1 can be easily adjusted.

Examples of the metal fluoride used as the amorphized metal material include LaF ₃ , BaF ₂ , Na ₅ Al ₃ F ₁₄ , Na ₃ AlF ₆ , AlF ₃ , MgF ₂ , CaF ₂ , CeF ₃ , NdF ₃ , YF ₃ etc. are mentioned.

Furthermore, examples of the metal nitride used as the amorphized metal material include Si ₃ N ₄ and AlN. Among these, Si ₃ N ₄ is preferable. Since Si ₃ N ₄ has a high hardness, it is possible to improve the scratch resistance of the first high refractive index layer 3a by using Si ₃ N ₄ .
In the present invention, the metal nitride is used in the meaning including Si ₃ N ₄ .

In addition, these amorphized metal materials may be used independently, and 2 or more types may be used in arbitrary ratios and combinations.

In order to obtain the amorphized zinc sulfide, there is no particular limitation on the amount of the amorphized metal material contained with respect to the crystalline zinc sulfide. For example, although it cannot be generally described because it varies depending on the type of amorphized metal material, when SiO ₂ is used as the amorphized metal material, it is usually 1% by mass or more, more preferably 5% by mass with respect to crystalline zinc sulfide. % Or more and usually 99% by mass or less, and more preferably 95% by mass or less of SiO ₂ can be used to make amorphous zinc sulfide.

<First sulfurization prevention layer>
When the first high refractive index layer 3a contains zinc sulfide, as shown in FIG. 1A or C, the first antisulfuric layer 4a is provided between the first high refractive index layer 3a and the transparent metal layer 5.

As a material of the first sulfidation preventing layer 4a, for example, metal oxide, metal nitride, metal fluoride, or Zn can be used. Among these, Zn, a metal oxide containing Zn, or a metal oxide containing Ga is preferable. Only 1 type may be contained in the 1st

sulfurization prevention layer

4a, and 2 or more types may be contained. However, when the first high refractive index layer 3a, the first antisulfurization layer 4a, and the transparent metal layer 5 are continuously formed, the first antisulfurization layer 4a is composed of a compound capable of reacting with sulfur, It is preferable to contain a compound capable of adsorbing sulfur. When the material contained in the first sulfurization prevention layer 4a is a compound that reacts with sulfur, the reaction product with the sulfur preferably has a high visible light transmittance.

Examples of the metal oxide 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 , IGZO, M3 (registered trademark, manufactured by Merck Japan, a mixture of aluminum oxide and lanthanum oxide), In ₂ O _{5 and the} like can be mentioned.
Examples of the metal fluoride include LaF ₃ , BaF ₂ , Na ₅ Al ₃ F ₁₄ , Na ₃ AlF ₆ , AlF ₃ , MgF ₂ , CaF ₂ , CeF ₃ , NdF ₃ , YF _{3 and the} like.
Examples of the metal nitride include Si ₃ N ₄ and AlN.

Among them, as the material constituting the first anti-sulfuration layer 4a, preferably a metal oxide, in _{_{_{particular, ZnO, ITO, IGZO, Ga}}} 2 O 3, Nb 2 O 5, SnO 2, Y 2 O 3 and M3 (registered Trademark) is preferred. Thereby, adhesiveness with the zinc sulfide contained in the 1st high refractive index layer 3a or the 2nd high refractive index layer 3b can be improved, and durability can be improved more.

Here, the layer thickness of the first sulfidation preventing layer 4a is preferably a layer thickness capable of protecting the surface of the first high refractive index layer 3a from an impact when forming the transparent metal layer 5 described later. On the other hand, zinc sulfide that can be contained in the first high refractive index layer 4 a has high affinity with the metal contained in the transparent metal layer 5. Therefore, if the thickness of the first anti-sulfurization layer 4a is very thin and a part of the first high refractive index layer 3a is slightly exposed, the transparent metal layer 5 grows around the exposed part and is transparent. The metal layer 5 tends to be dense. That is, the first antisulfurization layer 4a is preferably relatively thin, preferably in the range of 0.1 to 10 nm, more preferably in the range of 0.5 to 5 nm, and still more preferably 1 to 3 nm. Is within the range. The layer thickness of the first sulfidation preventing layer 4a is measured with an ellipsometer.

≪Transparent metal layer≫
The transparent metal layer 5 is a layer for conducting electricity in the transparent conductor 1.

The transparent metal layer 5 preferably contains silver. From the viewpoint of obtaining high conductivity, the transparent metal layer 5 is preferably made of silver or an alloy containing 90 at% or more of silver.
As a metal combined with silver, for example, zinc, gold, copper, palladium, aluminum, manganese, bismuth, neodymium, molybdenum, nickel, iron, cobalt, tungsten, tantalum, chromium, indium, titanium, or the like can be used. Among these, copper, palladium, or bismuth is preferable. The transparent metal layer 5 may contain a simple substance or compound of silver and a simple substance or compound of copper, palladium, or bismuth, or is included in the form of an alloy of silver and at least one of these metals. However, it is preferably contained in the form of an alloy. Moreover, it is preferable that all of the materials constituting the transparent metal layer 5 are an alloy of silver and at least one of these metals. By including at least one of these metals in the transparent metal layer 5, it is possible to further improve the durability, peel resistance, and the like of the transparent conductor 1.
Further, for example, when the transparent metal layer 5 contains an alloy of silver and zinc, the sulfidation resistance of the transparent metal layer 5 can be improved. For example, when the transparent metal layer 5 contains an alloy of silver and gold, the salt resistance (NaCl) resistance of the transparent metal layer 5 can be improved. Furthermore, for example, when the transparent metal layer 5 contains an alloy of silver and copper, the oxidation resistance of the transparent metal layer 5 can be improved.

The plasmon absorption rate of the transparent metal layer 5 is preferably 10% or less (over the entire range) over a wavelength range of 400 to 800 nm, more preferably 7% or less, and even more preferably 5% or less. If there is a region having a large plasmon absorption rate in a part of the wavelength of 400 to 800 nm, the transmitted light of the transparent conductor 1 is easily colored.

The plasmon absorption rate at a wavelength of 400 to 800 nm of the transparent metal layer 5 is measured by the following procedure.

(I) Platinum palladium is formed to 0.1 nm on a glass substrate by a magnetron sputtering apparatus. The average thickness of platinum palladium is calculated from the formation rate of the manufacturer's nominal value of the sputtering apparatus. Thereafter, a film made of metal is formed with 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 light transmittance and light reflectance of the metal film are measured. Then, an absorptance (= 100− (light transmittance + light reflectance)) is calculated from the light transmittance and light reflectance at each wavelength, and this is used as reference data. The light transmittance and light reflectance are measured with a spectrophotometer.
(Iii) Subsequently, a transparent metal layer to be measured is formed on the same glass substrate. And about the said transparent metal layer, light transmittance and light reflectance are measured similarly. The reference data is subtracted from the obtained absorption rate, and the calculated value is defined as the plasmon absorption rate.

The layer thickness of the transparent metal layer 5 is preferably 10 nm or less, more preferably in the range of 3 to 9 nm, and still more preferably in the range of 5 to 8 nm. When the thickness of the transparent metal layer 5 is 10 nm or less, the optical admittance of the transparent conductor 1 is easily adjusted by the first high-refractive index layer 3a and the second high-refractive index layer 3b, and light reflection on the surface is prevented. It is easy to be suppressed. The layer thickness of the transparent metal layer 5 is measured with an ellipsometer.

The transparent metal layer 5 may be formed by any film formation method, but from the viewpoint of increasing the average transmittance of the transparent metal layer 5, it is preferably a layer formed by a sputtering method. It is preferable that the transparent metal layer 5 be a layer formed on an underlayer that can become a growth nucleus when forming the transparent metal layer 5. When the transparent metal layer 5 is a layer formed on the underlayer, the underlayer becomes a growth nucleus when the transparent metal layer 5 is formed, so that the transparent metal layer 5 tends to be a smooth layer. As a result, even if the transparent metal layer 5 is thin, plasmon absorption is less likely to occur.

In the sputtering method, when the layer is formed, the material collides with the deposition target at high speed, so that a dense and smooth film can be easily obtained and the light transmittance of the transparent metal layer 5 can be improved. Further, when the transparent metal layer 5 is a layer formed by sputtering, the transparent metal layer 5 is hardly corroded even in a high temperature and low humidity environment. The type of the sputtering method is not particularly limited, and ion beam sputtering, magnetron sputtering, reactive sputtering, bipolar sputtering, bias sputtering, RF sputtering, counter sputtering, and the like can be used. Among these, the transparent metal layer 5 is preferably a layer formed by RF sputtering or counter sputtering. When the transparent metal layer 5 is a layer formed by the RF sputtering method or the counter sputtering method, the transparent metal layer 5 becomes dense and the surface smoothness is likely to be increased. As a result, the surface electrical resistance of the transparent metal layer 5 can be further reduced, and the light transmittance can be improved.

<Second sulfurization prevention layer>
When the second high refractive index layer 3b contains zinc sulfide, as shown in FIG. 1B or C, a second antisulfurization layer 4b is provided between the transparent metal layer 5 and the second high refractive index layer 3b. Is preferred.
Since the second sulfidation preventing layer 4b is configured in the same manner as the first sulfidation preventing layer 4a, description of common points is omitted, and only points different from the first sulfidation preventing layer 4a are described below. .

The layer thickness of the second antisulfurization layer 4b is preferably a layer thickness that can protect the surface of the transparent metal layer 5 from an impact during the formation of the second high refractive index layer 3b. The metal contained in the transparent metal layer 5 and zinc sulfide that can be contained in the second high refractive index layer 3b have high affinity. Therefore, if the thickness of the second antisulfurization layer 4b is very thin and a part of the transparent metal layer 5 is slightly exposed, the transparent metal layer 5, the second antisulfurization layer 4b, and the second high refractive index layer. Adhesion with 3b tends to increase.
Therefore, the specific layer thickness of the second antisulfurization layer 4b is preferably in the range of 0.1 to 10 nm, more preferably in the range of 0.5 to 5 nm, and still more preferably 1 to 3 nm. Is within the range. The layer thickness of the second sulfurization preventing layer 4b is measured with an ellipsometer.

<Second high refractive index layer>
The second high refractive index layer 3b is a layer for adjusting the light transmittance (optical admittance) of the region where the transparent metal layer 5 is formed.
The second high-refractive index layer 3b is configured in the same manner as the first high-refractive index layer 3a. Therefore, description of common points is omitted, and only differences from the first high-refractive index layer 3a are described below. Explained.

As described above, the second high-refractive index layer 3b may contain zinc sulfide. If the second high-refractive index layer 3b contains zinc sulfide, the second metal layer 5b transmits moisture to the transparent metal layer 5. It is possible to suppress the corrosion of the transparent metal layer 5.

≪Physical properties of transparent conductor≫
The average transmittance of light at a wavelength of 450 to 800 nm of the transparent conductor according to the present invention is preferably 94% or more. When the average transmittance in the above wavelength range is 94% or more, the transparent conductor can be applied to applications requiring high transparency to visible light.

On the other hand, the average transmittance of light at a wavelength of 400 to 1000 nm of the transparent conductor is preferably 85% or more, more preferably 88% or more, and still more preferably 90% or more. When the average transmittance of light at a wavelength of 400 to 1000 nm is 85% or more, the present invention also relates to applications requiring transparency with respect to light in a wide wavelength range, such as a transparent conductive film for solar cells. A transparent conductor can be applied.

On the other hand, the average absorptance of light at a wavelength of 400 to 800 nm of the transparent conductor is preferably 10% or less, more preferably 8% or less, and still more preferably 7% or less.
Further, the maximum value of the light absorptance at a wavelength of 450 to 800 nm of the transparent conductor is preferably 15% or less, more preferably 10% or less, and further preferably 9% or less.
On the other hand, the average reflectance of light at a wavelength of 500 to 700 nm of the transparent conductor is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less.
The lower the average absorptance and average reflectance of the transparent conductor, the higher the aforementioned average transmittance.

The average transmittance and the average reflectance are preferably the average transmittance and the 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 average transmittance and average reflectance can be measured with a spectrophotometer by making measurement light incident from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent conductor. The average absorptance is calculated from a calculation formula of 100− (average transmittance + average reflectance).

The luminous reflectance of the transparent conductor is preferably 5% or less, more preferably 3% or less, and still more preferably 1% or less. The luminous reflectance is a Y value measured with a spectrophotometer (U4100: manufactured by Hitachi High-Technologies Corporation).

Further, the a ^* value and b ^* value in the L ^* a ^* b ^* color system of the transparent conductor are each preferably within ± 30, more preferably within ± 5.0, and ± 3. It is further preferably within 0, and particularly preferably within ± 2.0. When the a ^* value and b ^* value in the L ^* a ^* b ^* color system are within ± 30, the color is 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 value of the transparent conductor is preferably 50Ω / □ or less, and more preferably 30Ω / □ or less. A transparent conductor having a surface electrical resistance value of 50 Ω / □ or less can be applied to a transparent conductive panel for a capacitive touch panel. The surface electrical resistance value of the transparent conductor is adjusted by the thickness of the transparent metal layer and the like. The surface electrical resistance value of the transparent conductor is measured in accordance with, for example, JIS K7194, ASTM D257, and the like. It is also measured by a commercially available surface electrical resistivity meter.

≪Use of transparent conductor≫
The transparent conductor according to the present invention includes various types of optoelectronics such as liquid crystal, plasma, organic electroluminescence, field emission, various types of displays, touch panels, mobile phones, electronic paper, various solar cells, various electroluminescence dimming elements, etc. It can be preferably used for a substrate of a device.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

[Example 1]
On the cycloolefin film “ZEONOR Z14” (thickness: 50 μm) made by Nippon Zeon as a transparent substrate, the first high refractive index layer and the first sulfurization prevention are produced as follows using the production apparatus 300 shown in FIG. A transparent metal layer 101, a transparent metal layer, a second anti-sulfurization layer, and a second high-refractive index layer to produce transparent conductors 101 to 104, and the manufacturing apparatus 200 shown in FIG. In this way, the first high refractive index layer, the first antisulfurization layer, the transparent metal layer, the second antisulfurization layer, and the second high refractive index layer were formed, and the transparent conductors 105 to 108 were produced. As the target of 200, the split target shown in FIG. 4C was used.

≪Preparation of transparent conductor≫
(1) Production of Transparent Conductor 101 In the manufacturing apparatus 300, ZnS—SiO ₂ is used as the target 333 of the evaporation source 331, ZnO is used as the target 343 of the evaporation source 341, Ag is used as the target 353 of the evaporation source 351, and evaporation is performed. ZnO was used as the target 363 of the source 361, and ZnS—SiO ₂ was used as the target 373 of the evaporation source 371.
The conveyance speed of the transparent substrate was set to 0.20 m / min.

(1.1) Formation of First High Refractive Index Layer On a Nippon Zeon cycloolefin film “Zeonor Z14” (thickness 50 μm) as a transparent substrate, Ar 40.0 sccm, sputtering pressure 0.1 Pa, room temperature (25 ° C.) Then, ZnS—SiO ₂ was sputtered at an electric power input to the evaporation source 331 of 10 W / cm ² to form a first high refractive index layer having a layer thickness of 40.0 nm.
The width | variety (target length) in the board | substrate conveyance direction of the area | region facing the transparent substrate of the evaporation source 331 was 0.20 m.

(1.2) Formation of first sulfidation prevention layer On the first high refractive index layer, Ar 40.0 sccm, sputtering pressure 0.1 Pa, room temperature (25 ° C.), the electric power input to the evaporation source 341 is 1.2 W. ZnO was sputtered at / cm ² to form a first sulfidation preventive layer having a layer thickness of 2.4 nm.
The target length of the evaporation source 341 was 0.20 m.

(1.3) Formation of transparent metal layer On the first antisulfurization layer, Ar 40.0 sccm, sputtering pressure 0.1 Pa, room temperature (25 ° C.), the electric power input to the evaporation source 351 is 0.4 W / cm ^2. Then, a transparent metal layer having a layer thickness of 9.0 nm was formed by sputtering Ag.
The target length of the evaporation source 351 was 0.10 m.
Note that the target length of the transparent metal layer was controlled using an aperture limiting mask. Here, the width of the aperture limiting mask is the target length.

(1.4) Formation of second anti-sulfurization layer and second high-refractive index layer In the same manner as the first anti-sulfurization layer and the first high-refractive index layer, the

evaporation sources

361 and 371 sequentially form the transparent metal layer. The second sulfidation prevention layer and the second high refractive index layer were formed, and the transparent conductor 101 was produced.

(2) Production of Transparent Conductor 102 ZnS is used as the target 333 of the evaporation source 331, ZnO is used as the target 343 of the evaporation source 341, Ag is used as the target 353 of the evaporation source 351, and ZnO is used as the target 363 of the evaporation source 361. ZnS was used as the target 373 of the evaporation source 371.
The conveyance speed of the transparent substrate was set to 0.36 m / min.

(2.1) Formation of First High Refractive Index Layer On a Nippon Zeon cycloolefin film “Zeonor Z14” (thickness 50 μm) as a transparent substrate, Ar 40.0 sccm, sputtering pressure 0.1 Pa, room temperature (25 ° C.) Below, ZnS was sputtered at an electric power input to the evaporation source 331 of 10 W / cm ² to form a first high refractive index layer having a layer thickness of 40.0 nm.
The target length of the evaporation source 331 was 0.20 m.

(2.2) Formation of first sulfidation prevention layer On the first high refractive index layer, Ar 40.0 sccm, sputtering pressure 0.1 Pa, room temperature (25 ° C.), the amount of power supplied to the evaporation source 341 is 1.9 W. ZnO was sputtered at / cm ² to form a first sulfidation preventing layer having a layer thickness of 2.1 nm.
The target length of the evaporation source 341 was 0.20 m.

(2.3) Formation of Transparent Metal Layer On the first antisulfurization layer, Ar 40.0 sccm, sputtering pressure 0.1 Pa, room temperature (25 ° C.), the electric power input to the evaporation source 351 is 0.4 W / cm ^2. Then, Ag was sputtered to form a transparent metal layer having a layer thickness of 10.0 nm.
The target length of the evaporation source 351 was 0.20 m.
Note that the target length of the transparent metal layer was controlled using an aperture limiting mask. Here, the width of the aperture limiting mask is the target length.

(2.4) Formation of second antisulfurization layer and second high refractive index layer In the same manner as the first antisulfurization layer and the first high refractive index layer, the

evaporation sources

361 and 371 sequentially form the transparent metal layer. The second sulfidation prevention layer and the second high refractive index layer were formed, and the transparent conductor 102 was produced.

(3) Production of transparent conductor 103 In production of the transparent conductor 101, except that the input power amount at the time of forming the first and second antisulfurization layers, the input power amount at the time of forming the transparent metal layer, and the target length were changed. Similarly, a transparent conductor 103 was produced.

(4) Production of transparent conductor 104 Transparent conductor 104 was produced in the same manner as in production of transparent conductor 103, except that the target length was changed when forming the first and second sulfidation prevention layers.

(5) Production of Transparent Conductor 105 In the manufacturing apparatus 200 shown in FIG. 6, ZnS—SiO ₂ is used as the target 133 of each evaporation source 131, ZnO is used as the split target 153a of the evaporation source 151, Ag is used as the split target 153b. ZnO was used as the split target 153c, and ZnS—SiO ₂ was used as the target 173 of each evaporation source 171.
The conveyance speed of the transparent substrate was set to 0.40 m / min.

(5.1) Formation of First High Refractive Index Layer On a ZEON cycloolefin film “ZEONOR Z14” (thickness 50 μm) as a transparent substrate, Ar 40.0 sccm, sputtering pressure 0.1 Pa, room temperature (25 ° C.) Then, ZnS—SiO ₂ was sputtered at an electric power input to each evaporation source 131 at 10 W / cm ² to form a first high refractive index layer having a layer thickness of 40.0 nm.
The target length of the evaporation source 131 was 0.40 m.

(5.2) Formation of first anti-sulfuration layer, transparent metal layer and second anti-sulfur layer On the first high-refractive index layer, Ar 40.0 sccm, sputtering pressure 0.1 Pa, room temperature (25 ° C.), evaporation source 151 is sputtered at an input power amount of 1.9 W / cm ² to form a first antisulfurization layer having a thickness of 0.7 nm, a transparent metal layer having a thickness of 8.4 nm, and a first metal having a thickness of 0.7 nm. A disulfide prevention layer was formed.
The division target lengths corresponding to the first sulfidation prevention layer, the transparent metal layer, and the second sulfidation prevention layer of the evaporation source 151 were 0.08 m, 0.04 m, and 0.08 m, respectively.
Note that the target lengths of the first anti-sulfuration layer, the transparent metal layer, and the second anti-sulfur layer were controlled using an opening limiting mask. Here, the width of the aperture limiting mask is the target length.

(5.3) Formation of Second High Refractive Index Layer A second high refractive index layer is formed on each second antisulfurization layer by the respective evaporation sources 171 in the same manner as the first high refractive index layer. A body 105 was produced.

(6) Production of transparent conductor 106 Transparent conductor 106 was produced in the same manner as in production of transparent conductor 105, except that the amount of electric power applied to evaporation source 151 was changed as shown in Table 2.

(7) Production of transparent conductor 107 In production of the transparent conductor 106, the target lengths corresponding to the split targets 153a and 153c of the evaporation source 151, the first sulfidation prevention layer, the transparent metal layer, and the second sulfidation prevention layer are shown. A transparent conductor 107 was produced in the same manner except that the changes were made as described in 1 and 2.

(8) Production of transparent conductor 108 In production of the transparent conductor 105, the transport speed of the transparent substrate and the target length corresponding to the first sulfidation prevention layer, the transparent metal layer and the second sulfidation prevention layer of the evaporation source 151 are indicated. A transparent conductor 108 was produced in the same manner except that the changes were made as described in 1 and 2.

In addition, the layer thickness of each layer in the transparent conductors 101 to 108 is J.P. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

Moreover, the static formation speed at the time of forming each layer was calculated.
Here, the static deposition rate (nm / min) is the thickness of the layer actually deposited on the transparent substrate after the transparent substrate passes over the region facing the transparent substrate of the deposition source. When t (nm), the transport speed (constant speed) of the transparent substrate is R (m / min), and the width in the substrate transport direction of the region facing the transparent substrate of the film forming source is w (m), It is a value calculated by t × R) / w. Note that in the case where a film formation mask is provided, the width of the opening of the film formation mask in the substrate transport direction is w (m). The substrate transport direction is a direction substantially parallel to the surface of the film forming source facing the transparent substrate, and is a direction along the direction in which the transparent substrate is transported on the film forming source.

≪Evaluation of transparent conductor≫
(1) Measurement of light transmittance and absorptance (absorption loss) About each produced transparent conductor, the average transmittance | permeability, average reflectance, and average absorptance of light were measured as follows.

Matching oil (refractive index at 25 ° C. at 25 ° C. = 1.515) manufactured by Nikon Corporation is applied to the surface of each transparent conductor on the second high refractive index layer side, and the transparent conductor and a non-alkali glass substrate (EAGLE XG manufactured by Corning) (Thickness 7 mm × length 30 mm × width 30 mm)), and the transmittance and reflectance of the transparent conductor were measured from the non-alkali glass substrate side. At this time, measurement light (light having a wavelength of 450 to 800 nm) is incident from an angle inclined by 5 ° with respect to the normal line of the surface of the alkali-free glass substrate, and the spectrophotometer U4100 manufactured by Hitachi, Ltd. The transmittance (%) and the reflectance (%) were measured.
The average absorptance was calculated from a calculation formula of 100− (average transmittance + average reflectance).
The measurement results are shown in Table 2.

In addition, the average reflectance of the transparent conductor is the reflection at the interface between the non-alkali glass substrate and the atmosphere (4%), and the reflection at the interface between the transparent substrate of the transparent conductor and the atmosphere. A value obtained by subtracting (4%) was used.
Further, the transmittance of the transparent conductor is 8 in the measured value of the transmittance considering the reflection at the interface between the alkali-free glass substrate and the atmosphere and the reflection at the interface between the transparent substrate and the atmosphere of the transparent conductor. % Was added.

(2) Measurement of resistance value About each produced transparent conductor, Loresta EP MCP-T360 made from Mitsubishi Chemical Analytech was contacted, and the surface electrical resistance value (Ω / □) was measured.
The measurement results are shown in Table 2.

(3) Summary As is clear from Table 2, it was found that the transparent conductor 101 of the comparative example has a large amount of absorption loss and a low average light transmittance. The transparent conductor 102 of the comparative example which changed the material of the 1st and 2nd high refractive index layer, the transparent conductor 103 of the comparative example which changed the layer thickness of the transparent metal layer, and the layer thickness of the 1st and 2nd antisulfation layer And in 104, the situation was unchanged.
On the other hand, in the transparent conductors 105 to 108 of the present invention using the divided target, improvements were observed in the average light transmittance, the amount of absorption loss, and the resistance value.

From the above, it has a plurality of film forming steps for forming a thin film layer on a transparent substrate with a plurality of evaporation sources, and the target of at least one evaporation source is composed of at least two divided targets made of different materials. It was confirmed that the transparent conductor manufacturing method is useful for suppressing a decrease in light transmittance due to sulfidation of the transparent metal layer material.

The present invention can be particularly suitably used for providing a method for producing a transparent conductor that suppresses a decrease in light transmittance due to sulfidation of a transparent metal layer material.

DESCRIPTION OF SYMBOLS 1 Transparent conductor 2 Transparent substrate 3a 1st high refractive index layer 3b 2nd high refractive index layer 4a Sulfidation prevention layer (1st sulfurization prevention layer)
4b Anti-sulfur layer (second anti-sulfur layer)
5 transparent metal layer 100 manufacturing apparatus 110 vacuum chamber 120 unwinding chamber 130 first film forming chamber 131 evaporation source 132 sputtering cathode 133 target 140 first differential pressure chamber 150 second film forming chamber 151 evaporation source 152

sputtering cathodes

153a, 153b, 153c Division target 160 Second differential pressure chamber 170 Third film formation chamber 171 Evaporation source 172 Sputtering cathode 173 Target 180

Delivery roller

181, 183 Guide roller 182 Main roller 184 Take-up rollers 190 to 195 Partition 196 Partition plate 197 Holding shaft 200 Manufacturing apparatus 230 First film forming chamber 240 Second film forming chamber 250 Third film forming chamber 260 Fourth film forming chamber 270 Fifth film forming chamber 300

Manufacturing apparatuses

331, 341, 351, 361, 371

Evaporation sources

333, 343 353,3 3,373 targets A, B, C, D curve X conveying direction

Claims

A first high-refractive index layer, a transparent metal layer, and a second high-refractive index layer are sequentially laminated on a transparent substrate that is continuously transported, and further, the first high-refractive index layer and the second high-refractive index layer. A method for producing a transparent conductor, in which an anti-sulfurization layer is laminated between at least one rate layer and the transparent metal layer,
A plurality of film forming steps for forming a thin film layer on the transparent substrate by a plurality of evaporation sources;
A method for producing a transparent conductor, wherein the target of at least one of the evaporation sources is composed of at least two divided targets made of different materials.
2. The method of manufacturing a transparent conductor according to claim 1, wherein the at least two divided targets include a divided target that is a material of the anti-sulfurization layer and a divided target that is a material of the transparent metal layer. .
3. The method for producing a transparent conductor according to claim 2, wherein the divided target which is a material of the transparent metal layer is silver or an alloy containing silver.
4. The transparent conductor according to claim 2, wherein the split target that is a material of the sulfidation prevention layer is Zn, a metal oxide containing Zn, or a metal oxide containing Ga. 5. Method.