JP2015173050A - Method of producing transparent conductor and patterned transparent conductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a transparent conductor in which side surfaces of various functional layers have a pattern etched uniformly in the lamination direction and a patterned transparent conductor.SOLUTION: A method of producing a patterned transparent conductor having a transparent substrate, a first high-refractive-index layer, a transparent metal layer and a second high-refractive-index layer, in this order, and includes a step of forming the first high-refractive-index layer and the second high-refractive-index layer which contain a specified material higher in the refractive index to light of a specified wavelength than the transparent substrate, with at least one of the first and second high-refractive-index layers being a zinc sulfide containing layer containing zinc sulfide, and a step of etching collectively the first high-refractive-index layer, the transparent metal layer and the second high-refractive-index layer under a condition of a specified relationship between the etching rates of the first high-refractive-index layer and the second high-refractive-index layer and the etching rate of the transparent metal layer is specified.

Description

  The present invention relates to a transparent conductor manufacturing method and a patterned transparent conductor. More specifically, the present invention relates to a method of manufacturing a transparent conductor having a pattern in which side surfaces of various functional layers are uniformly etched in a stacking direction, and a patterned transparent conductor.

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

As a material constituting such a transparent conductive film, gold (Au), silver (Ag), platinum (Pt), copper (Cu), rhodium (Rh), palladium (Pd), aluminum (Al), chromium (Cr ) And other metals such as In ₂ O ₃ , CdO, CdIn ₂ O ₄ , Cd ₂ SnO ₄ , titanium oxide (TiO ₂ ), tin oxide (SnO ₂ ), zinc oxide (ZnO), ITO (Indium Tin Oxide), etc. 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 (hereinafter also referred to as “ITO film”) made of ITO having a high light transmittance is frequently used.

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

Therefore, it has been studied to use a vapor-deposited Ag film as a transparent conductive film (see, for example, Patent Document 1). In order to increase the light transmittance of the transparent conductor, an Ag layer made of an Ag film is formed of a layer having a high refractive index (for example, niobium oxide (Nb ₂ O ₅ ), IZO (Indium Zinc Oxide), ICO (Indium Cerium Oxide)). , A-GIO (Amorphous Gallium Indium Oxide), a layer made of ZnO, ITO, or the like) has also been proposed (see, for example, Patent Documents 2 to 4). Furthermore, it has also been proposed to sandwich the Ag layer with a zinc sulfide (ZnS) layer (see, for example, Non-Patent Documents 1 and 2).

However, as disclosed in Patent Documents 2 to 5 and Non-Patent Documents 1 to 3, for example, ITO / silver thin film / ITO, Nb ₂ O ₅ / silver thin film / IZO or ZnS / silver thin film / ZnS. The transparent conductor manufactured by the sputtering method has the following problems.

That is,
1) A transparent conductor in which an Ag layer is sandwiched between dielectric layers such as niobium oxide and IZO has a problem that moisture resistance is not sufficient. For this reason, when the transparent conductor is used in a high humidity environment, the Ag layer is corroded.
2) In the transparent conductor in which the Ag layer is sandwiched between the ZnS layers, the moisture resistance of the transparent conductor is sufficiently high. However, when the Ag layer is formed or when the ZnS layer is formed, Ag is sulfided and silver sulfide is formed. Prone to occur. As a result, there is a problem that the light transmittance of the transparent conductor is lowered. Furthermore, since ZnS tends to become a crystal | crystallization, there also existed a problem that a transparent conductor became easy to break as a result.
3) There was a problem that the flexibility of the formed transparent conductor was insufficient. For this reason, a crack etc. are easy to generate in the above-mentioned transparent conductor.

In order to solve the above problems 1) to 3), for example, a transparent conductor having a structure of ZnS—SiO ₂ / silver thin film / ZnS—SiO ₂ is conceivable (see, for example, Patent Document 5).
However, with such a configuration, the rate at which ZnS—SiO ₂ is etched (hereinafter also referred to as “etching rate”) is too high compared to Ag. There is a problem that a pattern in which the side surface of the functional layer is uniformly etched in the stacking direction cannot be processed. In addition, the above problem 2) that Ag is sulfided and silver sulfide is easily generated when the Ag layer is formed or the ZnS layer is formed cannot be solved.

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

Xuanjie Liu, et al, (2003). Thin Solid Films 441, 200-206 Optically transparent IR reflective heat mirror films of ZnS-Ag-ZnS, Bruce W. Smith, May 1989. Rochester Institute Of Technology Center For Imaging Science Transient Conductive Film Nb2O5 / Ag / IZO with an Anti-Reflection Design, Ywh-Tang Leu, et al. , SID 2012 DIGEST p. 352-353

  The present invention has been made in view of the above-described problems and situations, and a solution to that problem is a method for manufacturing a transparent conductor having a pattern in which side surfaces of various functional layers are uniformly etched in the stacking direction, and patterning. It is to provide a transparent conductor.

In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, the ratio of the etching rate of the first high refractive index layer and the second high refractive index layer and the etching rate of the transparent metal layer. If etching is performed under a condition where the value falls within a predetermined range, any material constituting the transparent conductor can be prevented from being shaved first, so any material constituting the transparent conductor remains extremely. Thus, the present inventors have found that a transparent conductor having a pattern in which the side surfaces of various functional layers are uniformly etched in the stacking direction can be manufactured.
That is, the said subject which concerns on this invention is solved by the following means.

1. A method for producing a transparent conductor, comprising producing a patterned transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order,
(A) a dielectric material or oxide semiconductor material having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm, and the first high refractive index layer and the second high refractive index layer; Forming at least one of the first high refractive index layer and the second high refractive index layer as a zinc sulfide-containing layer containing zinc sulfide (ZnS);
(B) The ratio value (E ₁ / E ₃ ) between the etching rate (E ₁ ) of the first high refractive index layer and the etching rate (E ₃ ) of the transparent metal layer is within the range of 0.002 to 350. and, within the scope of the second is the ratio of the values of the etching rate of the transparent metal layer and the etching rate of the high refractive index layer _{(E 2) (E 3)} (E 2 / E 3) 0.002~350 A step of collectively etching the first high refractive index layer, the transparent metal layer, and the second high refractive index layer under the conditions of:
The manufacturing method of the transparent conductor characterized by having.

  2. And further comprising a step of forming an antisulfurization layer containing at least one selected from metal oxide, metal fluoride, metal nitride and zinc (Zn) between the transparent metal layer and the zinc sulfide-containing layer. The method for producing a transparent conductor according to item 1, characterized in that:

3. The zinc sulfide-containing layer is at least one selected from titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), tin oxide (SnO ₂ ), and hafnium oxide (HfO ₂ ). The method for producing a transparent conductor according to item 1 or 2, wherein the metal oxide is contained.

4). A patterned transparent conductor manufactured by the method for manufacturing a transparent conductor according to any one of Items 1 to 3,
The first high refractive index layer and the second high refractive index layer contain a dielectric material or an oxide semiconductor material having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm, and At least one of the high refractive index layer and the second high refractive index layer is a zinc sulfide-containing layer containing zinc sulfide (ZnS);
The patterned transparent conductor, wherein the first high refractive index layer, the transparent metal layer, and the second high refractive index layer are partially etched.

  5. A sulfide prevention layer containing at least one selected from a metal oxide, a metal fluoride, a metal nitride, and zinc (Zn) is provided between the transparent metal layer and the zinc sulfide-containing layer. 5. The patterned transparent conductor according to item 4.

6). The zinc sulfide-containing layer is at least one selected from titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), tin oxide (SnO ₂ ), and hafnium oxide (HfO ₂ ). 6. The patterned transparent conductor according to item 4 or 5, characterized by containing a metal oxide.

By the above means of the present invention, it is possible to provide a method for producing a transparent conductor having a pattern in which side surfaces of various functional layers are uniformly etched in the laminating direction, and a patterned transparent conductor.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

1 and 2 are schematic views showing an example of patterning a transparent conductor having a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order by etching. 1A and FIG. 2A show the transparent conductor before etching, and FIG. 1B and FIG. 2B show the transparent conductor after etching.
In general, in addition to etching in the vertical direction (direction in which layers are stacked), side etching also proceeds. The side etching referred to here is etching that proceeds in the horizontal direction with respect to the transparent substrate. If the upper layer is not completely dissolved, the etching of the lower layer may not proceed. However, in reality, the liquid soaks downward when the upper layer is being etched, and the etching of the lower layer starts. Is done.
For this reason, when the etching rates of the first high-refractive index layer, the second high-refractive index layer, and the transparent metal layer are greatly different from each other, the above-described side etching proceeds excessively, for example, the transparent metal layer of FIG. As shown in FIG. 3, an extremely remaining layer is formed as compared with other layers. As a result, it is presumed that it becomes difficult to produce a transparent conductor having a pattern in which the side surfaces of various functional layers are uniformly etched in the stacking direction.
However, the ratio value (E ₁ / E ₃ ) between the etching rate (E ₁ ) of the first high refractive index layer and the etching rate (E ₃ ) of the transparent metal layer is in the range of 0.002 to 350, and , conditions within the range of the second ratio value of the etching rate of the transparent metal layer and the etching rate of the high refractive index layer _{(E 2) (E 3)} (E 2 / E 3) is 0.002 to 350 When the etching is performed, the three layers of the first high refractive index layer, the transparent metal layer, and the second high refractive index layer are etched (melted) at the same rate. Therefore, any material does not remain extremely, and a pattern in which the side surfaces of various functional layers are uniformly etched in the stacking direction as shown in FIG. 2B can be engraved.

Schematic diagram showing an example of etching a transparent conductor Schematic diagram showing another example of etching a transparent conductor Schematic sectional view showing an example of the layer structure of a transparent conductor Schematic diagram showing an example of a pattern composed of a conductive region and an insulating region of a transparent conductor Process flow diagram showing an example of patterning a transparent conductor using etching Graph showing admittance locus in an example of transparent conductor Schematic diagram illustrating an example of a transparent conductor evaluation method according to an embodiment Schematic diagram of another example illustrating a method for evaluating a transparent conductor according to an example Graph showing the relationship between the content ratio of SiO _{2 to} ZnS and the etching rate

The method for producing a transparent conductor according to the present invention includes a transparent conductor for producing a patterned transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order. (A) a dielectric material or an oxide semiconductor material having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm, and a first high refractive index layer and a second high refractive index layer Forming at least one of the refractive index layers as a zinc sulfide-containing layer containing zinc sulfide (ZnS), and forming a first high refractive index layer and a second high refractive index layer; and (b) a first high refractive index layer. the etching rate of the refractive index layers _{(E 1)} and a second ratio of the values of the etching rate of the high refractive index layer _{(E 2)} and the etching rate of the transparent metal layer _{(E 3) (E 1 /} E 3 and _E 2 / The first high refractive index layer under the condition that E ₃ ) is within a predetermined range And a step of collectively etching the transparent metal layer and the second high refractive index layer. This feature is a technical feature common to the inventions according to claims 1 to 6.

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

In the present invention, the zinc sulfide-containing layer is composed of titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), tin oxide (SnO ₂ ), and hafnium oxide (HfO _2). It is preferable to contain at least one metal oxide selected from
Thereby, the transparent conductor which has the pattern by which the side surface of various functional layers was etched uniformly in the lamination direction can be manufactured.

  Further, as the patterned transparent conductor of the present invention, the first high-refractive index layer and the second high-refractive index layer have a higher refractive index than that of the transparent substrate with respect to light having a wavelength of 570 nm, or an oxidation material. A zinc sulfide-containing layer containing a zinc semiconductor (ZnS), wherein at least one of the first high-refractive index layer and the second high-refractive index layer Preferably, the layer, the transparent metal layer and the second high refractive index layer are partially etched. Thereby, the patterned transparent conductor which has the pattern by which the side surface of various functional layers was etched uniformly in the lamination direction can be provided.

  Furthermore, the patterned transparent conductor of the present invention contains at least one selected from metal oxide, metal fluoride, metal nitride, and zinc (Zn) between the transparent metal layer and the zinc sulfide-containing layer. It is preferable to have a sulfidation preventing layer. Thereby, the sulfidation of the transparent metal layer can be prevented, and the light transmittance can be improved.

Further, as the patterned transparent conductor of the present invention, the zinc sulfide-containing layer is composed of titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), tin oxide (SnO ₂ ). And at least one metal oxide selected from hafnium oxide (HfO ₂ ). This is preferable because a patterned transparent conductor having a pattern in which side surfaces of various functional layers are uniformly etched in the stacking direction can be provided.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.
In addition, the value of the refractive index measured in the environment of 25 degreeC is used with the refractive index as used in the field of this invention. The refractive index can be determined by measuring using a commercially available ellipsometer.

[Outline of transparent conductor]
FIG. 3 shows an example of the layer structure of the patterned transparent conductor (hereinafter also simply referred to as “transparent conductor”) according to the present invention. The transparent conductor 10 according to the present invention includes transparent substrate 1 / first high refractive index layer 2 / transparent metal layer 3 / second high refractive index layer 4. In the transparent conductor 10 according to the present invention, either or both of the first high refractive index layer 2 and the second high refractive index layer 4 are zinc sulfide-containing layers containing zinc sulfide (ZnS). . Between the zinc sulfide-containing layers 2 and 4 and the transparent metal layer 3, an antisulfurization layer 5 (5a and 5b) is included.

  Here, when one of the first high refractive index layer 2 and the second high refractive index layer 4 is a zinc sulfide-containing layer, the first high refractive index layer 2 or the second high refractive index layer 2 that is a zinc sulfide-containing layer. Between the refractive index layer 4 (hereinafter also referred to as “zinc sulfide-containing layer 2 or 4”) and the transparent metal layer 3, an antisulfurization layer 5 is included. On the other hand, when both the first high-refractive index layer 2 and the second high-refractive index layer 4 are zinc sulfide-containing layers, the sulfide is interposed between any one of the zinc sulfide-containing layers 2 or 4 and the transparent metal layer 3. The prevention layer 5 may be included, but from the viewpoint of sufficiently increasing the light transmittance of the transparent conductor 10, the sulfide prevention layer 5 is provided between each of the zinc sulfide-containing layers 2 and 4 and the transparent metal layer 3. Is preferably included. That is, it is preferable that the sulfuration preventing layer 5 is included between the first high refractive index layer 2 and the transparent metal layer 3 and between the transparent metal layer 3 and the second high refractive index layer 4.

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

  When the transparent metal layer is formed on the zinc sulfide-containing layer (first high refractive index layer 2) by a vapor deposition method such as sputtering, the unreacted sulfur component in the zinc sulfide-containing layer is The material (metal material) is repelled into the forming atmosphere. Then, the ejected sulfur component reacts with the metal derived from the transparent metal layer, and metal sulfide is deposited on the zinc sulfide-containing layer. Further, when the zinc sulfide-containing layer and the transparent metal layer are continuously formed, the sulfur component contained in the atmosphere in which the zinc sulfide-containing layer is formed remains in the transparent metal layer atmosphere. And this sulfur component and the metal derived from a transparent metal layer react, and metal sulfide deposits on a zinc sulfide content layer.

  On the other hand, when the zinc sulfide-containing layer (second high refractive index layer 4) is formed on the transparent metal layer, the metal in the transparent metal layer is expelled into the forming atmosphere by the material of the zinc sulfide-containing layer. The ejected metal reacts with the sulfur component, and metal sulfide is deposited on the surface of the transparent metal layer. Furthermore, a metal sulfide is generated on the surface of the transparent metal layer also when the surface of the transparent metal layer comes into contact with the sulfur component in the forming atmosphere.

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

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

  In the transparent conductor 10 according to the embodiment of the present invention, as shown in FIG. 3, the first high refractive index layer, the transparent metal layer, and the second high refractive index layer are partially etched and patterned into a desired shape. ing. In the transparent conductor according to the embodiment of the present invention, the region a where the transparent metal layer 3 is laminated is a region where electricity is conducted (hereinafter also referred to as “conduction region a”). On the other hand, the region b where the transparent metal layer 3 is not included is the insulating region b.

  The pattern composed of the conductive region a and the insulating region b is appropriately selected according to the use of the transparent conductor 10. For example, when the transparent conductor 10 is applied to an electrostatic touch panel, as shown in FIG. 4, the pattern includes a plurality of conductive regions a and line-shaped insulating regions b that divide the conductive regions a. sell.

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

(Method for producing transparent conductor of the present invention)
The method for producing a transparent electrode according to the present invention includes a transparent conductor for producing a patterned transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order. A manufacturing method comprising: (a) a dielectric material or an oxide semiconductor material having a refractive index larger than that of a transparent substrate with respect to light having a wavelength of 570 nm; and a first high refractive index layer and a second high refractive index Forming at least one of the refractive index layers as a zinc sulfide-containing layer containing zinc sulfide (ZnS), and forming a first high refractive index layer and a second high refractive index layer; and (b) first high refractive index. The ratio value (E ₁ / E ₃ ) of the etching rate (E ₁ ) of the refractive index layer and the etching rate (E ₃ ) of the transparent metal layer is in the range of 0.002 to 350, and the second high refractive index layer Etching Rate (E ₂ ) and Transparent Metal Layer Etching Rate The first high-refractive index layer, the transparent metal layer, and the second high-refractive index layer are collectively etched under the condition that the ratio (E ₂ / E ₃ ) to the degree (E ₃ ) is in the range of 0.002 to 350. And a process.

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

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

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

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

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

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

(Process of forming a transparent metal layer)
In this step, a transparent metal layer is formed on the first sulfurization prevention layer.
The method for forming the transparent metal layer in this step is not particularly limited, and a general vapor deposition method such as a vacuum deposition method, an ion plating method, a plasma CVD method, and a thermal CVD method can be employed in addition to the sputtering method. .

(Step of forming the second sulfurization prevention layer)
In this step, the second sulfurization preventing layer is formed on the transparent metal layer.
This step is a step of forming a sulfidation preventing layer containing at least one selected from metal oxide, metal fluoride, metal nitride, and zinc (Zn) between the transparent metal layer and the zinc sulfide-containing layer. .

  The method for forming the second antisulfurization layer in this step is not particularly limited, and other than the above-described sputtering method, a general vapor deposition method such as a vacuum deposition method, an ion plating method, a plasma CVD method, and a thermal CVD method can be used. A membrane method can be employed.

(Step of forming the second high refractive index layer)
In this step, a second high refractive index layer is formed on the second sulfurization prevention layer.
When this second high refractive index layer contains zinc sulfide (ZnS), this step contains a dielectric material or oxide semiconductor material having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm, In addition, at least one of the first high refractive index layer and the second high refractive index layer is a zinc sulfide-containing layer containing zinc sulfide (ZnS), and the first high refractive index layer and the second high refractive index layer are used. Is a step of forming.

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

(Patterning process)
In this step, the layer (including at least the first high refractive index layer, the transparent metal layer, and the second high refractive index layer) formed on the transparent substrate is patterned into a desired shape. Thereby, the patterned transparent conductor which concerns on this invention can be manufactured. The patterning method is not particularly limited as long as etching is performed. For example, a photolithography method can be employed.
Hereinafter, a case where a photolithography method is employed as an example of the patterning process will be described.

  Photolithographic methods that can be employed in the present invention include, for example, resist coating such as curable resin, preheating, exposure, development (removal of uncured resin), rinsing, etching treatment with an etching solution, and resist stripping. In this way, the layer formed on the transparent substrate can be processed into a desired pattern.

  In the present invention, a conventionally known general photolithography method can be appropriately used. For example, as the resist, either positive or negative resist can be used. In addition, after applying the resist, preheating or prebaking can be performed as necessary. At the time of exposure, a pattern mask having a desired pattern may be disposed, and light having a wavelength suitable for the resist used, generally ultraviolet rays, electron beams, or the like may be irradiated thereon. After the exposure, development is performed with a developer suitable for the resist used. After the development, the resist pattern is formed by stopping the development with a rinse solution such as water and washing. Next, the formed resist pattern is pre-processed or post-baked as necessary, and then is etched with an etching solution described later to dissolve the intermediate layer in a region not protected by the resist and remove the silver thin film electrode. I do. After etching, the remaining resist is removed to obtain a transparent electrode having an intended pattern. As described above, the photolithography method applied to the present invention is a method generally recognized by those skilled in the art, and the specific application mode is easily selected by those skilled in the art according to the intended purpose. be able to.

  Next, an electrode pattern forming method applicable to the present invention will be described with reference to the drawings.

  FIG. 5 is a process flow diagram showing an example of forming an electrode pattern on the transparent conductor of the present invention by a photolithography method.

  As a first step, as shown in FIG. 5A, on the transparent substrate 2, the first high refractive index layer 2, the first sulfidation preventing layer 5a, the transparent metal layer 3, the second sulfidation preventing layer 5b, 2 A transparent conductor 10 in which the high refractive index layer 4 is laminated in this order is produced.

  Next, it is preferable to subject the transparent conductor 10 to ultrasonic cleaning before forming the resist film in FIG. As ultrasonic cleaning, for example, ultrasonic cleaning and washing with pure water are performed several times using a detergent clean-through KS-3030 manufactured by Kao Corporation, and then water is blown off with a spin coater and dried in an oven.

Next, in the resist film forming step shown in FIG. 5B, a resist film 6 made of a photosensitive resin composition or the like is uniformly coated on the transparent conductor 10. As the photosensitive resin composition, a negative photosensitive resin composition or a positive photosensitive resin composition can be used. As the resist, for example, OFPR-800LB manufactured by Tokyo Ohka Kogyo Co., Ltd. can be used.
As a coating method, it is applied on the transparent conductor 10 by a known method such as micro gravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, etc., and heated by a hot plate, an oven or the like. It can be pre-baked in the apparatus. The pre-baking can be performed, for example, using a hot plate or the like within a range of 50 to 150 ° C. for 30 seconds to 30 minutes.

Next, in the exposure step shown in FIG. 5C, an exposure machine 8 such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner is used through a mask 7 formed with a predetermined electrode pattern. The resist film 6a to be removed in the next step is irradiated with light of about 10 to 4000 J / m ² (wavelength 365 nm exposure conversion). The exposure light source is not limited, and ultraviolet rays, electron beams, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used.

  Next, in the developing step shown in FIG. 5D, the exposed transparent conductor 10 is immersed in a developing solution to dissolve the resist film 6a to be removed from the light-irradiated region. As the developer, for example, when a positive photosensitive resin composition is used as a resist, a developer for positive photoresist “Tokuso SD” series (tetramethylammonium hydroxide) manufactured by Tokuyama Corporation should be used. Can do.

  As a developing method, it is preferable to immerse in a developer for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide. Examples thereof include aqueous solutions containing one or more quaternary ammonium salts such as side and choline. After development, it is preferable to rinse with water, and then dry baking may be performed within a range of 50 to 150 ° C.

(Batch etching process)
In this step, the range of the ratio of the value of the etching rate of the first transparent metal layer etching rate of the high refractive index layer _{(E 1) (E 3)} (E 1 / E 3) is from 0.002 to 350, and, second ratio value of the etching rate of the high refractive index layer _{(E 2)} and the etching rate of the transparent metal layer _{(E 3) (E 2 /} E 3) is in the condition within the range of 0.002 to 350 The first high refractive index layer, the transparent metal layer, and the second high refractive index layer are collectively etched. Specifically, as shown in FIG. 5E, an etching process using an etchant 9 is performed. The collective etching means that the first high refractive index layer, the transparent metal layer, and the second high refractive index layer are etched together in one process using the same kind of etching solution.

Applicable etchant to the present invention, the etching rate of the first etch rate of the high refractive index layer (E ₁₎ and the second etch rate of the high refractive index layer (E ₂₎ and the transparent metal layer (E ₃₎ The ratio values (E ₁ / E ₃ and E ₂ / E ₃ ) are not particularly limited as long as the conditions satisfy the range of 0.002 to 350, but preferably within the range of 1 to 20, More preferably, it exists in the range of 3-7.
Specifically, a liquid containing an inorganic acid or an organic acid is preferable, and examples thereof include oxalic acid, hydrochloric acid, acetic acid, and phosphoric acid, and oxalic acid, acetic acid, and phosphoric acid are particularly preferable. Moreover, a commercial item can also be used as an etching liquid, for example, Pure Etch DE100, Clean etch 100, and Clean etch 102 by Hayashi Junyaku Kogyo Co., Ltd., Kanto Chemical development product mixed acid SEA-5, mixed acid SEA-1, etc. Can be used.

(Measurement of etching rate)
The etching rate according to the present invention is measured, for example, as follows.
For example, a film having a thickness of 30 to 400 nm and a diameter of 30 cm is formed on a glass with a material constituting a layer whose etching rate is to be measured. Next, the half of the film is masked, and the other half is immersed in an etching solution as it is. The decrease in film thickness after a certain time is measured, and the decrease in film thickness per unit time is taken as the etching rate according to the present invention. In addition, it is preferable to implement the temperature of etching liquid within the range of 25-45 degreeC, More preferably, it exists in the range of 25-35 degreeC.
In addition, for the film thickness measurement, for example, an Olympus USPM-RUIII reflectometer can be used, and the film thickness can be calculated from the reflectivity of the film.

  As a specific etching process, for example, the transparent conductor 10 having the resist film 6 is immersed in an etching solution containing an organic acid or the like, and the electrode unit EU in the insulating region b not protected by the resist film 6 is dissolved. Then, the electrode unit EU of the conduction region a protected by the resist film 6 is formed as a predetermined electrode pattern. The etching time varies depending on the type of acid to be applied, but it is preferably adjusted within 3 seconds at the earliest and within 10 minutes at the latest, and more preferably within the range of 30 to 120 seconds.

  Finally, as shown in FIG. 5 (f), the resist film remover was etched using, for example, acetone, sodium hydroxide solution, or commercially available N-300 manufactured by Nagase ChemteX Corporation. A transparent conductor having an electrode pattern can be produced by immersing the transparent conductor and removing the resist film 6.

  Next, each component used for the manufacturing method of the transparent conductor of this invention is explained in full detail.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The dielectric material or the oxide semiconductor material included in the second high refractive index layer 4 may be ZnS. When the second high refractive index layer 2 contains zinc sulfide, the second high refractive index layer is a zinc sulfide-containing layer according to the present invention. The details of the zinc sulfide-containing layer will be described later.

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

(Zinc sulfide containing layer)
Dielectric material or oxide semiconductor contained in the first high-refractive index layer 2 and the second high-refractive index layer 4 (hereinafter, collectively referred to as “high-refractive index layer” unless otherwise required) The material can also be zinc sulfide (ZnS). When zinc sulfide (ZnS) is contained in the high refractive index layer, the first high refractive index layer 2 and the second high refractive index layer 4 are the zinc sulfide-containing layer 2 and the zinc sulfide-containing layer 4 according to the present invention. (Hereinafter, they are collectively referred to as “zinc sulfide-containing layer” when there is no need for distinction).
When ZnS is included in the first high refractive index layer 2 to form the zinc sulfide-containing layer 2, moisture hardly penetrates from the transparent substrate 1 side, and corrosion of the transparent metal layer 3 is suppressed.
Further, when ZnS is included in the second high refractive index layer 4 to form the zinc sulfide-containing layer 4, it is possible to suppress moisture from being transmitted from the second high refractive index layer 4 side and to prevent corrosion of the transparent metal layer 3. .
The first high refractive index layer 2 and the second high refractive index layer 4 are preferably formed of the same material, and both the first high refractive index layer 2 and the second high refractive index layer 4 are zinc sulfide-containing layers. Preferably there is.

The zinc sulfide-containing layer may contain only ZnS, and may contain other materials together with ZnS.
The material contained together with ZnS in the zinc sulfide-containing layer is a metal oxide or silicon dioxide (SiO ₂ ) that can be the dielectric material or the oxide semiconductor material, and is particularly preferably SiO ₂ . When SiO ₂ is contained together with ZnS, the zinc sulfide-containing layer is likely to be amorphous, and the flexibility of the transparent conductor is likely to be enhanced.

In particular, the zinc sulfide-containing layer is selected from titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), tin oxide (SnO ₂ ), and hafnium oxide (HfO ₂ ). It is preferable to contain at least one kind of metal oxide, and it is particularly preferable to contain SiO ₂ . In addition, it is guessed that this is because there are many cases where the etching solution generally used is an acidic solution. For this reason, it is speculated that ZnS contained in the zinc sulfide-containing layer has a high etching rate because of its low acid resistance. Therefore, ZnS—TiO ₂ , ZnS—Nb ₂ O ₅ , ZnS—Ta ₂ O ₅ , ZnS—SnO ₂ , ZnS—HfO _2, etc., become materials having a relatively low etching rate with an acidic solution (high acid resistance). When the zinc sulfide-containing material is contained in the zinc sulfide-containing layer, it is presumed that the difference in etching rate between the layers constituting the transparent conductor can be avoided. Thereby, the transparent conductor which has the pattern by which the side surface of various functional layers was etched uniformly in the lamination direction can be manufactured.

When the zinc sulfide-containing layer contains other materials together with ZnS, the amount of the other materials is preferably 0.1 to 95% by mass with respect to the total number of moles of the material constituting the zinc sulfide-containing layer. Furthermore, since the etching rate can be made more appropriate, it is more preferably 5 to 50% by mass.
Particularly preferably, the content is 10 to 30% by mass. If the content of the other material with respect to ZnS is 30% or less, it is possible to avoid a possibility that the etch rate rapidly increases. If the content is 10% or more, the etch rate rapidly decreases. The risk of doing so can be avoided.

[Transparent metal layer]
The transparent metal layer 3 is a layer for conducting electricity in the transparent conductor 10.

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

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

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

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

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

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

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

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

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

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

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

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

  The first antisulfurization layer 5a may contain only one compound selected from metal oxides, metal fluorides, metal nitrides, and zinc (Zn), and may contain two or more compounds. Preferably contains a metal oxide, and further a Zn-containing metal oxide. However, when the first high refractive index layer 2, the first sulfidation preventing layer 5a, and the transparent metal layer 3 are continuously formed, the metal oxide can react with sulfur or adsorb sulfur. Preferably. When the metal oxide is a compound that reacts with sulfur, the reaction product of the metal oxide and sulfur preferably has high visible light permeability.

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

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

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

  The second antisulfurization layer 5b may contain only one kind of compound selected from metal oxide, metal fluoride, metal nitride and zinc (Zn), and may contain two or more kinds. Preferably, a metal oxide, and further a Zn-containing metal oxide is preferably contained. The metal oxide, metal nitride, and metal fluoride may be the same as the metal oxide, metal nitride, and metal fluoride contained in the first high refractive index layer 2 described above.

  The thickness of the second antisulfurization layer 5b is preferably a thickness that can protect the surface of the transparent metal layer 3 from an impact when the second high refractive index layer 4 is formed. On the other hand, the metal contained in the transparent metal layer 3 and ZnS that can be contained in the second high refractive index layer 4 have high affinity. Therefore, if the thickness of the second antisulfuration layer 5b is very thin and a part of the transparent metal layer 3 is slightly exposed from the second antisulfurization layer 5b, the transparent metal layer 3 and the second antisulfurization layer 5b And the second high-refractive-index layer 4 are likely to be improved in adhesion. Therefore, the specific thickness of the second antisulfurization layer 5b is preferably 0.1 to 10 nm, more preferably 0.5 to 5 nm, and further preferably 1 to 3 nm. The thickness of the second sulfurization preventing layer 5b is measured with an ellipsometer.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

上記の式に基づけば、｜Ｙ_ｅｎｖ−Ｙ_Ｅ｜が０に近い程、透明導電体（透過領域ａ）の表面の反射率Ｒが低くなる。 ≪About optical admittance of transparent conductor≫
The reflectance R of the surface of the transparent conductor transmission region a (the surface of the transparent conductor opposite to the transparent substrate) is determined by the optical admittance Y _{env of the} medium on which light is incident and the surface of the transparent conductor transmission region a. determined from the equivalent admittance _{Y E.} Here, the medium on which the light is incident refers to a member or environment through which light incident on the transparent conductor passes immediately before the incident; a member or environment made of an organic resin. The relationship between the optical admittance Y _{env of the} medium on which light is incident and the equivalent admittance Y _E of the surface of the transparent conductor is expressed by the following equation.

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

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

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

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

・ When the xth layer is an ideal metal layer

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

In FIG. 6, for example, transparent substrate / first high refractive index layer (ZnS—SiO ₂ ) / first antisulfurization layer (ITO) / transparent metal layer (Ag) / second high refractive index layer (ZnS—SiO ₂ ) The admittance locus | trajectory of wavelength 570nm of the conduction | electrical_connection area | region a of a transparent conductor provided with was shown. The horizontal axis of the graph is the real part when the optical admittance Y of the region is represented by x + iy; that is, x in the equation, and the vertical axis is the imaginary part of the optical admittance; that is, y in the equation. In the transparent conductor of the above example, the first sulfidation preventing layer is sufficiently thin, and thus its optical admittance can be ignored.

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

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

上記関係式に基づけば、透明金属層表面の光学アドミッタンスＹ１及びＹ２の実数部（ｘ_１及びｘ_２）が大きくなれば、透明金属層の電場強度Ｅが小さくなり、電場損失（光の吸収）が抑制される。すなわち、透明導電体の光透過性が十分に高まる。 The following relational expression is established between the admittance Y at the interface between the layers constituting the transparent conductor and the electric field strength E existing in each layer.

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

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

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

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

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

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

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

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

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

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

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

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

  The surface electrical resistance value of the conductive region a of the transparent conductor is preferably 50Ω / □ or less, more preferably 30Ω / □ or less. A transparent conductor having a surface electric resistance value of 50 Ω / □ or less in the conduction region can be applied to a transparent conductive panel for a capacitive touch panel. The surface electrical resistance value of the conduction region a is adjusted by the thickness of the transparent metal layer and the like. The surface electrical resistance value of the conduction region a is measured according to, 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 conductors described above are used in various optoelectronic devices such as liquid crystal, plasma, organic electroluminescence, field emission, and other types of displays, as well as touch panels, mobile phones, electronic paper, various solar cells, and various electroluminescence dimming elements. It can be preferably used for a substrate or the like.

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

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

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

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

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

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

First, the etching rate was measured about the material which can form a 1st high refractive index layer, a transparent metal layer, and a 2nd high refractive index layer as follows.
In this example, the etching rate was measured for an Ag alloy (an alloy containing 1.5 atomic% of Au and 0.5 atomic% of Cu in Ag), Ag, ZnS, IGZO, ZnS- _{TiO 2, ZnS-Nb 2 O} 5, ZnS-Ta 2 O 5, ZnS-SnO 2, ZnS-HfO 2, ZnS-SiO 2, ZnO, a _ZnS-Ga 2 _{O 3.}

Incidentally, ZnS—TiO ₂ , ZnS—Nb ₂ O ₅ , ZnS—Ta ₂ O, which are materials composed of ZnS and additives, used in the following transparent conductor [1] to transparent conductor [25]. ₅ , ZnS—SnO ₂ , ZnS—HfO ₂ , ZnS—SiO _2, and ZnS—Ga ₂ O ₃ were all used with a molar ratio of ZnS and additive of 80:20.

The etching rate was measured as follows.
On the glass, a film made of the above-described material is formed with a thickness of 30 to 400 nm and a diameter of 30 cm, half of the film is masked, and the other half is left as it is. C.). The decrease in film thickness after 2 seconds or 300 seconds was measured, and the decrease in film thickness per unit time was calculated as the etching rate.
In addition, the film thickness was calculated from the reflectivity of the film by using an Olympus USPM-RUIII reflectometer.

In addition, the etching liquid used for the measurement of an etching rate is the following liquid A-liquid E.
Liquid A Pure Pure DE 100 manufactured by Hayashi Junyaku
Liquid B: Clean etch 100 made by Hayashi Junyaku
Liquid C: Clean Etch 102 made by Hayashi Junyaku
Liquid D ··· Mixed acid SEA-5 developed by Kanto Chemical
Liquid E: Kanto Chemical Co., Ltd. developed product mixed acid SEA-1

  Table 1 shows the measurement results of the etching rate for each film forming material.

[Production of transparent conductor]
In this example, each layer constituting the transparent conductor was continuously laminated by a roll-to-roll method to produce a laminate. Then, the following transparent conductor [1] to transparent conductor [30] were produced by patterning this laminate.
The refractive indexes shown below are all values at a temperature of 25 ° C.

<Preparation of transparent conductor [1]>
On the cycloolefin polymer (COP) (transparent substrate, refractive index with respect to light having a wavelength of 570 nm is 1.52), the following layers were laminated to produce a transparent conductor [1].

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

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

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

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

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

(Patterning of transparent conductor)
Next, in accordance with the patterning method shown in FIG. 5, a pattern having the conductive region a and the insulating region b shown in FIG. 3 was formed.

  Before forming the resist film 6, the produced transparent conductor [1] was subjected to ultrasonic cleaning treatment. As a cleaning solution, an ultrasonic cleaning process was performed at 25 ° C. for 4 minutes using a detergent “Clean Through KS-3030 (10%)” manufactured by Kao Corporation. Subsequently, after washing 5 times with pure water at 25 ° C., ultrasonic washing was performed twice with pure water at 25 ° C. for 4 minutes. Finally, water was scattered with a spin coater and then dried in an oven.

  Next, on the cleaned transparent conductor [1], OFPR-800LB manufactured by Tokyo Ohka Kogyo Co., Ltd. was applied as a resist by spin coating, and dried at 2000 rpm for 30 seconds to form a resist film 6 having a thickness of 1 μm. Formed.

  Next, ultraviolet rays were irradiated through the mask 7 under conditions of 60 mJ, and development was performed using a developer for positive photoresist “Tokuso SD-1” (tetramethylammonium hydroxide) manufactured by Tokuyama Corporation as a developer. .

  Next, batch etching was performed with the above-described liquid C (liquid temperature: 45 ° C.) to form a pattern in which line-shaped conductive regions a and insulating regions b were alternately arranged. The line widths of the conduction region a and the insulation region b were both 20 μm.

  Finally, the remaining resist film 6 was peeled off using acetone to produce a patterned transparent conductor [1].

<Preparation of Transparent Conductor [2] to Transparent Conductor [24]>
A transparent conductor patterned in the same manner as the transparent conductor [1] except that the transparent substrate, the transparent metal layer, the first high refractive index layer and the second high refractive index layer are made of the materials shown in Table 2. [2] to transparent conductor [24] were prepared.

<Preparation of transparent conductor [25]>
The first anti-sulfurization layer and the second anti-sulfurization layer were not formed, but the transparent substrate, the transparent metal layer, the first high refractive index layer, and the second high refractive index layer were formed using the materials shown in Table 2. A patterned transparent conductor [25] was produced in the same manner as the transparent conductor [1].

<Preparation of Transparent Conductor [26] to Transparent Conductor [30]>
For the transparent conductor [26] to the transparent conductor [30], the ratio (molar ratio) of ZnS to SiO ₂ was 96: 4, 90:10, 70:30, 60:40 and 30: respectively. The patterned transparent conductor [26] to transparent conductor [30] were produced in the same manner as the transparent conductor [16] except that 70 was desired.
The etching rates of the high refractive index layer in the transparent conductor [26] to the transparent conductor [30] were 5.37, 12.45, 16.21, 9.75, and 0.11, respectively.

In addition, the refractive index with respect to the light of wavelength 570nm of the material used for the transparent substrate, the 1st high refractive index layer, and the 2nd high refractive index layer is as follows.
COP ... 1.53
Glass film ... 1.52
PET ... 1.64
PC ... 1.59
ZnS-TiO ₂ ... 2.38
ZnS-Nb ₂ O ₅ ... 2.35
ZnS-Ta ₂ O ₅ ... 2.21
ZnS-SnO ₂ ... 2.14
ZnS-HfO ₂ ... 2.21
_ZnS-SiO 2 ... 2.15
ZnS-Ga ₂ O ₃ ... 2.17
IGZO ... 2.09

<Evaluation of Transparent Conductor [1] to Transparent Conductor [30]>
Evaluation about transparent conductor [1]-transparent conductor [30] was implemented as follows.

(Measurement of light transmittance)
About each produced said transparent conductor, the light transmittance and the light absorptivity were measured as follows.
Matching oil (refractive index = 1.52 manufactured by Nikon Corporation) was applied to the surface of each transparent conductor on the second high refractive index layer side. Then, a transparent conductor and a non-alkali glass substrate (EAGLE XG (thickness 7 mm × length 30 mm × width 30 mm) manufactured by Corning) were bonded together, and the transmittance of the transparent conductor was measured from the alkali-free glass substrate side. At this time, measurement light (for example, light having a wavelength of 400 to 800 nm) is incident on the conduction region from an angle inclined by 5 ° with respect to the normal line of the surface of the alkali-free glass substrate, and manufactured by Hitachi High-Technologies Corporation: The light transmittance was measured with a spectrophotometer U4100.
The light transmittance in Table 3 is equivalent to the transmittance obtained by subtracting the surface reflectance lost at the air-alkali glass interface and the surface reflectance lost at the transparent conductor substrate-air interface (corresponding to the internal transmittance). .) Value.
The evaluation results are shown in Table 3. The evaluation criteria are as follows.
◎ ... 90% or more ○ ... 80% or more but less than 90% × ... less than 80%

(Etching evaluation)
7 and 8 are schematic diagrams for explaining a method for evaluating etching of a transparent conductor, and are plan views of the transparent conductor manufactured as described above.
First, patterning is performed while observing any three points with a line length of 50 μm at the boundary between the conductive region a and the insulating region b, so that the minimum width between the conductive regions a adjacent to both sides of the insulating region b is 20 μm. When it reaches, patterning is stopped. At this time, the maximum PV width of the etching line in the conductive region a adjacent to both sides of the insulating region b was evaluated as a total value. When a plurality of etching lines are observed, the maximum width including all the etching lines is measured. The etching line referred to here is a continuous line generated by etching in the horizontal direction (in the direction of arrow LR shown in FIGS. 7 and 8) with respect to the transparent substrate. The maximum PV width refers to the maximum deviation in the horizontal direction.
The evaluation results are shown in Table 3. The evaluation criteria are as follows.
◎ ... Total less than 5μm ○… Total 5μm or more and less than 10μm △… Total 10μm or more and less than 15μm ×… Total 15μm or more

(Summary)
Table 3 shows that according to the present invention, a transparent conductor having a pattern in which the side surfaces of various functional layers are uniformly etched in the stacking direction can be produced.

Note that, as described above, the etching rates of the high refractive index layers in the transparent conductor [26] to the transparent conductor [30] are 5.37, 12.45, 16.21, 9.75, 0.85, respectively. 11. From this result, it is presumed that the relationship between the content ratio of the compound added to ZnS and the etching rate is as shown in the graph of FIG.
From this, when the content of SnO ₂ with respect to ZnS is around 10 to 30% by mass, the etching rate does not become too small and is relatively stable. It is believed that there is. That is, it is presumed that if the content of other materials with respect to ZnS is 30% or less, the risk of a sharp increase in etch rate can be avoided, and if it is 10% or more, the risk of a rapid decrease in etch rate can be avoided. .
In fact, as shown in Table 3, the transparent conductor [16], the transparent conductor [27], and the transparent conductor [28, compared to the transparent conductor [26], the transparent conductor [29], and the transparent conductor [30]. ] Had good etching evaluation.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 1st high refractive index layer (zinc sulfide content layer)
3 Transparent metal layer 4 Second high refractive index layer (zinc sulfide-containing layer)
DESCRIPTION OF SYMBOLS 5 Antisulfide layer 5a 1st antisulfide layer 5b 2nd antisulfide layer 6 Resist film 6a Resist film to remove 7 Mask 8 Exposure machine 9 Etching liquid 10 Transparent conductor

Claims (6)

A method for producing a transparent conductor, comprising producing a patterned transparent conductor having at least a transparent substrate, a first high refractive index layer, a transparent metal layer, and a second high refractive index layer in this order,
(A) a dielectric material or oxide semiconductor material having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm, and the first high refractive index layer and the second high refractive index layer; Forming at least one of the first high refractive index layer and the second high refractive index layer as a zinc sulfide-containing layer containing zinc sulfide (ZnS);
(B) The ratio value (E ₁ / E ₃ ) between the etching rate (E ₁ ) of the first high refractive index layer and the etching rate (E ₃ ) of the transparent metal layer is within the range of 0.002 to 350. and, within the scope of the second is the ratio of the values of the etching rate of the transparent metal layer and the etching rate of the high refractive index layer _{(E 2) (E 3)} (E 2 / E 3) 0.002~350 A step of collectively etching the first high refractive index layer, the transparent metal layer, and the second high refractive index layer under the conditions of:
The manufacturing method of the transparent conductor characterized by having.   And further comprising a step of forming an antisulfurization layer containing at least one selected from metal oxide, metal fluoride, metal nitride and zinc (Zn) between the transparent metal layer and the zinc sulfide-containing layer. The method for producing a transparent conductor according to claim 1. The zinc sulfide-containing layer is at least one selected from titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), tin oxide (SnO ₂ ), and hafnium oxide (HfO ₂ ). The method for producing a transparent conductor according to claim 1, wherein the metal oxide comprises: A patterned transparent conductor manufactured by the method for manufacturing a transparent conductor according to any one of claims 1 to 3,
The first high refractive index layer and the second high refractive index layer contain a dielectric material or an oxide semiconductor material having a refractive index larger than that of the transparent substrate with respect to light having a wavelength of 570 nm, and At least one of the high refractive index layer and the second high refractive index layer is a zinc sulfide-containing layer containing zinc sulfide (ZnS);
The patterned transparent conductor, wherein the first high refractive index layer, the transparent metal layer, and the second high refractive index layer are partially etched.   The anti-sulfurization layer containing at least one selected from a metal oxide, a metal fluoride, a metal nitride, and zinc (Zn) is provided between the transparent metal layer and the zinc sulfide-containing layer. Item 5. The patterned transparent conductor according to item 4. The zinc sulfide-containing layer is at least one selected from titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), tin oxide (SnO ₂ ), and hafnium oxide (HfO ₂ ). The patterned transparent conductor according to claim 4, wherein the patterned transparent conductor is contained.

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