JP2020121546A - Laminate and manufacturing method of the same - Google Patents

Abstract

To suppress in a laminate which includes a substrate, an electrode layer and an oxide layer, dissolution of the oxide layer in image development or resist peeling, and an increase in a reflectance ratio caused thereby, and peeling of the electrode layer.SOLUTION: A laminate 10 comprises: a substrate 12; an electrode layer 16 formed on the substrate 12; and a first oxide layer 18 formed on the surface of the electrode layer 16, and/or a second oxide layer 14 inserted into between the substrate 12 and the electrode layer 16. Each of the first oxide layer 18 and the second oxide layer 14 contains at least Cu and Zn, and has an abundance ratio of CuO of 45% or more. The first oxide layer 18 and the second oxide layer 14 are obtained by sputtering in a decompressed oxidative atmosphere, using a Cu-Zn-A alloy target containing Cu and Zn, and if necessary, an adhesiveness-improving element A selected from the group consisting of B, Mg, Al, Ca, Ti, Cr, Mn, Ni and Sn.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminate and a method for manufacturing the same, more specifically, a laminate that can be used for a touch panel or the like, in which an electrode layer on a substrate surface and an oxide layer for reducing the reflectance of the electrode layer are provided. The present invention relates to a formed laminate and a method for manufacturing the same.

The touch panel that allows input on the image display screen by the sensor arranged on the front of the screen display device is used in addition to operation images of bank ATMs, ticket vending machines, car navigation systems, PDAs, copiers, etc. in recent years due to its ease of use. It is widely used in various screen devices such as telephones and tablet PCs. Examples of the method include a resistance film method, an electrostatic capacity method, an optical method, an ultrasonic surface acoustic wave method, and a piezoelectric method. Among them, the capacitance type is used in mobile phones, tablet PCs, and the like because of its multi-touch capability, excellent responsiveness, and low cost.

The capacitive touch panel sensor has a structure in which two types of transparent conductive films (sensors) are orthogonal to each other via a glass substrate, a film substrate, an organic film, a SiO ₂ film, or the like. Above all, a resin film substrate such as polyethylene terephthalate (PET) is excellent in handleability. When the finger is moved closer, the capacitance between the conductive films, which are the sensors, changes, and the touched portion is detected. The transparent conductive film has a problem of high electrical resistivity and close contact with the underlying substrate.

Since the current transparent conductive film has a large electric resistivity, it is difficult to enlarge the screen. This is because when the screen has a large size with the same electrical resistivity, it takes a long time to detect a change in capacitance from the transparent conductive film.
In addition, in a sensor using a transparent electrode, it is necessary to repeat film formation and etching of the adhesion layer, the conductive layer, and the barrier layer in addition to the transparent electrode layer, which causes a problem of restrictions on the film forming apparatus and complicated man-hours. Will be higher and manufacturers will be greatly restricted.
Further, since ITO is expensive, an inexpensive material system is required.

Therefore, attention has been paid to an alloy film that can also serve as a sensor and a conductive layer. This is because instead of the transparent conductive film, an alloy film is formed, and the front part of the image display device has an invisible line width (mesh pattern) so that the sensor and conductive layer can replace the transparent electrode. It plays a role at the same time. If the alloy has excellent adhesiveness to the substrate, the adhesive layer is not necessary, and the manufacturing process can be significantly shortened because the alloy 1 layer can be manufactured by film formation and etching.

It is considered to use Ag, Al, and Cu-based metals and alloys as the metal of the mesh. However, the thin metal wires made of these metals or alloys have lower electrical resistivity than ITO, but are opaque and have metallic luster. Therefore, there is a problem that the light from the outside is reflected by the thin metal wires and the reflected light reduces the visibility of the display unit of the touch panel.

Therefore, in order to solve this problem, various proposals have been conventionally made. For example, Patent Document 1 discloses a structure in which a light absorption layer made of Mo-based oxynitride, Al-based oxynitride, or Cu-based oxynitride is formed on the surface of a conductive film.
The document describes that by introducing a light-absorbing pattern on the viewing side of the user, reflection by the conductive pattern can be prevented without affecting the conductivity of the conductive pattern.

Further, in Patent Document 2, a base material, a first metal layer laminated on the base material, and a surface of the first metal layer opposite to the base material or between the first metal layer and the base material are laminated. And a second metal layer formed of a Cu alloy containing Zn, wherein the second metal layer has a light reflectance of 20% or less.
In the document, when the second metal layer having a low reflectance is formed on the upper surface of the first metal layer or between the first metal layer and the base material, the reflection of light by the first metal layer is suppressed, which is favorable. It is described that it is possible to secure good visibility.

As described in Patent Documents 1 and 2, in order to suppress reflection of light from a layer (electrode layer) made of metal thin wires, a layer for suppressing reflection of light (oxidation on the light incident surface side). Object layer) is performed. Such an electrode layer and an oxide layer are usually produced by using a photolithography technique. Further, various materials have been conventionally proposed as materials for the oxide layer. Among these, an oxide layer made of a Cu alloy oxide has an advantage that it has a lower reflectance than an oxide layer made of another material (for example, Cu oxide).
However, the oxide layer made of the Cu alloy oxide may be dissolved by the alkaline solution used during development or resist stripping. Therefore, when the oxide layer is formed on the surface of the electrode layer, the electrode layer may be exposed during development or resist stripping. Further, when an oxide layer is formed at the interface between the substrate and the electrode layer, the oxide layer (adhesion layer) may be dissolved and the electrode layer may be peeled off during development or resist stripping.

Special table 2013-540331 gazette JP, 2016-085598, A

The problem to be solved by the present invention is to provide an electrode layer on the surface of the substrate, and a laminate in which an oxide layer for reducing the reflectance of the electrode layer is formed, the oxide layer at the time of development or resist stripping. It is to suppress melting and increase in reflectance and peeling of the electrode layer due to the melting.
Further, another problem to be solved by the present invention is to provide a method for producing a laminate capable of producing such a laminate.

In order to solve the above problems, the gist of the laminated body according to the present invention is to have the following configuration.
(1) The laminated body is
Board,
An electrode layer formed on the substrate,
It comprises a first oxide layer formed on the surface of the electrode layer and/or a second oxide layer formed at the interface between the substrate and the electrode layer.
(2) The first oxide layer is
Including a first main element containing at least Cu and Zn,
The ratio of the amount of CuO present to the total amount of Cu compounds contained in the first oxide layer (the ratio of CuO present) is 45% or more.
(3) The first main element is
0.1≦Zn≦10.0 at%, and
0≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
And the balance consists of Cu and inevitable impurities.
(4) The second oxide layer is
Including a second main element containing at least Cu and Zn,
The ratio of the amount of CuO present to the total amount of Cu compounds contained in the second oxide layer (the ratio of CuO present) is 45% or more.
(5) The second main element is
0.1≦Zn≦10.0 at%, and
0≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
And the balance consists of Cu and inevitable impurities.

Further, the gist of the method for producing a laminated body according to the present invention is to have the following configuration.
(1) The method for manufacturing the laminate is
An electrode layer forming step of forming an electrode layer on the substrate,
A first oxide layer is formed on the surface of the electrode layer to form a laminated film, and/or a second oxide layer is formed on the surface of the substrate before the electrode formation step. Forming a second oxide layer to obtain the laminated film;
A developing step of forming a photoresist film on the surface of the laminated film and developing it;
An etching step of etching the laminated film using the photoresist film as a mask,
And a resist stripping step of stripping the photoresist film.
(2) In the first oxide layer forming step,
0.1≦Zn≦10.0 at%, and
0≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
Using a Cu alloy target (A) containing
The first oxide layer is formed by sputtering in a reduced pressure oxidizing atmosphere having an O ₂ fraction of 35% or more and an N ₂ fraction of less than 1%.
(3) In the second oxide layer forming step,
0.1≦Zn≦10.0 at%, and
0≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
With a Cu alloy target (B) containing
The second oxide layer is formed by sputtering in a reduced pressure oxidizing atmosphere having an O ₂ fraction of 35% or more and an N ₂ fraction of less than 1%.

A Cu-Zn-A-based oxide film is formed by sputtering using a Cu-Zn-A alloy (CZA) target containing Cu and Zn and, if necessary, an adhesion improving element A such as Mg or Al. When the (CZA-O film) is formed, when the film formation is performed in a reduced pressure oxidizing atmosphere having a relatively high O ₂ fraction and a relatively low N ₂ fraction, the abundance ratio of CuO is high. A CZA-O film (that is, a small proportion of Cu ₂ O present) is obtained. An oxide film containing a large amount of CuO is difficult to dissolve in an alkaline solution. Therefore, when such a CZA-O film is used as an oxide layer, dissolution of the oxide layer at the time of development or peeling of the resist, and increase in reflectance and peeling of the electrode layer due to this can be suppressed. ..

It is a cross-sectional schematic diagram of the laminated body which concerns on this invention. It is a schematic diagram of a developing process, an etching process, and a resist stripping process. It is a diagram showing the relationship between O ₂ minutes rate and composition ratio of each element at the time of film formation. It is a diagram showing the relationship between the existing ratio of O ₂ partial rate and Cu compounds during film formation.

An embodiment of the present invention will be described in detail below.
[1. Laminate]
FIG. 1 shows a schematic sectional view of a laminate according to the present invention. In FIG. 1, the laminate 10 is
Substrate 12;
An electrode layer 16 formed on the substrate 12,
A first oxide layer 18 formed on the surface of the electrode layer 16 and/or a second oxide layer 14 formed at the interface between the substrate 12 and the electrode layer 16;
Equipped with.

In addition, in FIG. 1, the stacked body 10 includes both the first oxide layer 18 and the second oxide layer 14, but either one can be omitted. That is, “the electrode layer 16 is formed on the substrate 12 ”includes the case in which the substrate 12/the electrode layer 16 is laminated in this order, and the substrate 12/the second oxide layer 14/the electrode layer 16 in this order. Both cases that are stacked are included.

[1.1. substrate]
The material of the substrate 12 is not particularly limited, and various materials can be used according to the purpose. When manufacturing a touch panel using the laminate 10 according to the present invention, a transparent material is usually used for the substrate 12.

As the substrate 12, for example,
(A) A resin substrate made of polyethylene terephthalate (PET), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polycarbonate (PC), polymethylmethacrylate (PMMA), polyimide (PI), etc.
(B) A glass substrate made of soda lime glass, Tempax glass, Pyrex (registered trademark) glass, quartz glass, or the like,
and so on. The substrate 12 is particularly preferably a PET film substrate. This is because it is particularly easy to handle.

[1.2. Electrode layer]
[1.2.1. composition]
The electrode layer 16 is formed on the substrate 12 in a predetermined pattern. The material of the electrode layer 16 is not particularly limited and may be any material having a low electric resistivity. Examples of the material of the electrode layer 16 include Cu, Cu alloy, Al, and Al alloy.

[1.2.2. thickness]
The thickness of the electrode layer 16 is not particularly limited, and an optimum thickness can be selected according to the purpose. The thickness of the electrode layer 16 is usually about 0.1 μm to 1.0 μm.

[1.3. First oxide layer]
[1.3.1. Overview]
The first oxide layer 18 is for suppressing reflection of light incident from the first oxide layer 18 side. The first oxide layer 18 is formed on the surface of the electrode layer 16. Since the first oxide layer 18 comes into contact with the alkaline solution at the time of development and resist stripping, it is necessary to have resistance to the alkaline solution.

As described below, the first oxide layer 18 uses a Cu—Zn—A alloy (CZA) target containing Cu and Zn and, if necessary, the adhesion improving element A in a reduced pressure oxidizing atmosphere. It is formed by spattering. Therefore, the first oxide layer 18 is made of a Cu-Zn-A-based oxide film (CZA-O film) containing the first main element containing at least Cu and Zn.
Here, the “adhesion improving element A” is an element that contributes to improving the adhesiveness of the first oxide layer 18 and reducing the reflectance, and is B, Mg, Al, Ca, Ti, Cr, Mn, Ni. , And one or more elements selected from the group consisting of Sn.
The “first main element” is an element derived from the CZA target used for forming the first oxide layer 18, and is an element other than O.

[1.3.2. Oxygen content]
As described later, in order to obtain high resistance to an alkaline solution, it is necessary to increase the proportion of CuO present in the first oxide layer 18. For that purpose, the first oxide layer 18 needs to contain a predetermined amount of oxygen. By using the method described below, the first oxide layer 18 having an oxygen content of 50 at% to 70 at% is obtained.

[1.3.3. Existence ratio of CuO]
When the first oxide layer 18 is formed by sputtering using a CZA target in a reduced pressure oxygen atmosphere, various Cu compounds containing O are generated in the first oxide layer 18. Examples of such Cu compounds include CuO, Cu ₂ O, CuCO ₃ , Cu(OH) ₂ . Of these, CuCO ₃ and Cu(OH) ₂ are impurity phases formed by the impurity gas contained in the sputtering atmosphere. The less these are, the better, but they do not significantly affect the resistance to an alkaline solution.

On the other hand, Cu ₂ O is a phase generated when the O ₂ fraction in the sputtering atmosphere is excessively low or the N ₂ fraction is excessively large. Cu ₂ O has a great influence on the resistance to an alkaline solution. In general, the greater the proportion of Cu ₂ O contained in the first oxide layer 18, the lower the resistance to an alkaline solution.

In order to obtain high resistance to an alkaline solution, the first oxide layer 18 needs to have a CuO content of 45% or more. The abundance ratio of CuO is preferably 50% or more, and more preferably 60% or more.
Here, the “abundance ratio of CuO” refers to the ratio of the abundance of CuO to the total abundance of Cu compounds (excluding intermetallic compounds) contained in the first oxide layer 18. The method for measuring the abundance is not particularly limited, and various methods can be selected according to the purpose.
For example, when the abundance is measured by XPS analysis, when the detected Cu compounds are CuO, Cu ₂ O, CuCO ₃ , and Cu(OH) ₂ , the abundance ratio (X) of CuO is It is represented by (1).

X=[CuO]×100/Y (1)
However,
Y=[CuO]+[Cu ₂ O]+[CuCO ₃ ]+[Cu(OH) ₂ ],
[Z] is the abundance of compound Z determined by XPS analysis.

[1.3.4. Composition ratio of first main element]
The first oxide layer 18 is formed using a CZA target having a predetermined composition, and thus contains the first main element derived from the CZA target. Further, the composition ratio of the first main element contained in the first oxide layer 18 becomes substantially equal to the composition ratio of the CZA target used.

Specifically, the first main element is
0.1≦Zn≦10.0 at%, and
0≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
And the balance consists of Cu and inevitable impurities.
The content of the adhesion-promoting element A contained in the first main element is
0.1≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
Is preferred. The reason for limiting each element will be described later.

[1.3.5. thickness]
The thickness of the first oxide layer 18 is not particularly limited, and an optimum thickness can be selected according to the purpose. The thickness of the first oxide layer 18 is usually about 0.01 μm to 0.1 μm.

[1.4. Second oxide layer]
[1.4.1. Overview]
The second oxide layer 14 is for suppressing the reflection of light incident from the substrate 12 side and for improving the adhesion between the substrate 12 and the electrode layer 16. The second oxide layer 14 is formed at the interface between the substrate 12 and the electrode layer 16 as needed. The composition of the second oxide layer 14 may be the same as or different from that of the first oxide layer 18.

Similarly to the first oxide layer 18, the second oxide layer 14 uses a Cu—Zn—A alloy (CZA) target that contains Cu and Zn and, if necessary, the adhesion improving element A, It is formed by sputtering in a reduced pressure oxidizing atmosphere. Therefore, the second oxide layer 14 is formed of a Cu-Zn-A-based oxide film (CZA-O film) containing the second main element containing at least Cu and Zn.
Here, the “adhesion improving element A” is an element that contributes to improving the adhesiveness of the second oxide layer 14 and reducing the reflectance, and is B, Mg, Al, Ca, Ti, Cr, Mn, Ni. , And one or more elements selected from the group consisting of Sn.
The “second main element” is an element derived from the CZA target used for forming the second oxide layer 14, and is an element other than O.

[1.4.2. Oxygen content]
The second oxide layer 14 may be dissolved by side etching during development or resist stripping. Further, when the second oxide layer 14 is dissolved, the electrode layer 16 may peel off. Therefore, the second oxide layer 14 also needs to have high resistance to alkali.
In order to obtain high resistance to an alkaline solution, it is necessary to increase the proportion of CuO present in the second oxide layer 14. For that purpose, the second oxide layer 14 needs to contain a predetermined amount of oxygen. By using the method described below, the second oxide layer 14 having an oxygen content of 50 at% to 70 at% is obtained.

[1.4.3. Existence ratio of CuO]
In order to obtain high resistance to an alkaline solution, the second oxide layer 14 needs to have a CuO content of 45% or more. The abundance ratio of CuO is preferably 50% or more, and more preferably 60% or more. The details of the proportion of CuO present are as described above, and thus the description thereof is omitted.

[1.4.4. Composition ratio of second main element]
The second oxide layer 14 also contains a second main element derived from the CZA target because the second oxide layer 14 is also formed using a CZA target having a predetermined composition. Further, the composition ratio of the second main element contained in the second oxide layer 14 becomes substantially equal to the composition ratio of the CZA target used.

Specifically, the second main element is
0.1≦Zn≦10.0 at%, and
0≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
And the balance consists of Cu and inevitable impurities.
The content of the adhesion improving element A contained in the second type element is
0.1≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
Is preferred. The reason for limiting each element will be described later.

[1.4.5. thickness]
The thickness of the second oxide layer 14 is not particularly limited, and an optimum thickness can be selected according to the purpose. The thickness of the second blackened layer 14 is usually about 0.01 μm to 0.1 μm.

[2. target]
In the present invention, both the first oxide layer 18 and the second oxide layer 14 are formed by sputtering in a reduced pressure oxygen atmosphere using a Cu—Zn—A alloy (CZA) target having a predetermined composition. Manufactured. The CZA target used for manufacturing the oxide layer contains the following elements, and the balance is Cu and inevitable impurities. The types of additional elements, the ranges of their components, and the reasons for their limitation are as follows.

[2.1. Constituent elements]
(1) 0.1≦Zn≦10.0 at%:
Zn has the effect of improving the adhesion to the substrate of the touch panel sensor such as a resin film or a glass substrate (hereinafter sometimes simply referred to as a substrate) without significantly increasing the electrical resistivity of the oxide layer. .. In order to obtain such an effect, the Zn content needs to be 0.1 at% or more. The Zn content is more preferably 0.6 at% or more, and further preferably 2.0 at% or more.

On the other hand, if the Zn content is excessive, the electrical resistivity of the oxide layer becomes too high. Therefore, the Zn content needs to be 10.0 at% or less. The Zn content is more preferably 6.0 at% or less, and further preferably 5.0 at% or less.
The Zn content is particularly preferably 2.0≦Zn≦6.0 at %.

(2) 0≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%:
As described above, “adhesion improving element A (hereinafter, also simply referred to as “element A”)” is selected from the group consisting of B, Mg, Al, Ca, Ti, Cr, Mn, Ni, and Sn. Any one or more of the elements described above. Since any of the elements A contributes to the improvement of the adhesion of the oxide layer and the reduction of the reflectance, it can be added if necessary. In order to obtain high adhesion and low reflectance, the total content of the element A is preferably 0.1 at% or more. The total content of the element A is more preferably more than 0.5 at %. Most preferably, it is 1.0 at% or more.

On the other hand, if the total content of the element A becomes excessive, the electrical resistivity becomes too high, and the hot workability deteriorates. Therefore, the total content of the element A is preferably 10.0 at% or less. The total content of the element A is preferably 6.0 at% or less, more preferably 4.0 at% or less.
In particular, 2.0≦Zn≦6.0 at% and 1.0≦element A≦6.0 at% are preferable.

[B. Component balance: A/Zn ratio]
The element A has a function of forming a concentrated layer containing a larger amount of Zn and the element A near the interface between the substrate 12 and the second oxide layer 14 during the heat treatment. Further, the element A not consumed for forming the concentrated layer forms a compound with Zn.
When the total content of the element A becomes excessive as compared with the Zn content, the element A that has not been consumed for forming the concentrated layer or the compound remains in the Cu matrix. When the residual amount of the element A becomes excessive, the electrical resistivity of the Cu matrix increases.
In order to suppress the increase in the electrical resistivity of the Cu alloy film, the ratio (=A/Zn ratio) of the total content (at %) of the element A to the Zn content (at %) is 2.0 or less. preferable. The A/Zn ratio is more preferably 0.5 or less.

[3. Manufacturing method of laminated body]
The manufacturing method of the laminated body 10 according to the present invention,
An electrode layer forming step of forming the electrode layer 16 on the substrate 12,
Prior to the first oxide layer forming step of forming the first oxide layer 18 on the surface of the electrode layer 16 to obtain a laminated film and/or the electrode forming step, the second oxide layer 14 is formed on the surface of the substrate 12. Forming a second oxide layer to obtain a laminated film,
A developing step of forming a photoresist film on the surface of the laminated film and developing it;
An etching step of etching the laminated film using the photoresist film as a mask,
And a resist stripping step of stripping the photoresist film.

[3.1. Second oxide layer forming step]
First, the second oxide layer 14 is formed on the surface of the substrate 12 (second oxide layer forming step). As described above, either the second oxide layer forming step or the first oxide layer forming step can be omitted. Specifically, the second oxide layer 14 is formed by using a CZA target (B) having a predetermined composition and performing sputtering in a reduced pressure oxygen atmosphere. As a sputtering method, either a DC sputtering method or an RF sputtering method may be used.

[3.1.1. CZA target (B)]
Since the details of the CZA target (B) are as described above, the description is omitted.

[3.1.2. Reduced pressure oxidizing atmosphere]
Sputtering is performed in a reduced pressure oxidizing atmosphere. The “oxidizing atmosphere” refers to an atmosphere in which the O ₂ fraction is 35% or more, the N ₂ fraction is less than 1%, and the balance is a rare gas and inevitable impurities. "Depressurized" refers to a pressure below atmospheric pressure.

If the O ₂ fraction in the atmosphere is too low, the proportion of CuO in the second oxide layer 14 decreases. Therefore, the O ₂ fraction in the atmosphere needs to be 35% or more. The O ₂ fraction is preferably 50% or more.
Similarly, if the N ₂ fraction in the atmosphere is too high, the proportion of CuO in the second oxide layer 14 decreases. Therefore, the N ₂ fraction in the atmosphere should be less than 1%. The lower the N ₂ fraction, the better.

The pressure during sputtering is not particularly limited, and the optimum pressure can be selected according to the purpose. The pressure during sputtering is usually about 0.1 Pa to 1.0 Pa.

[3.2. Electrode layer forming process]
Next, if necessary, after forming the second oxide layer 14 on the surface of the base material 12, the electrode layer 16 is formed on the substrate 12 (electrode layer forming step). The forming method and forming conditions of the electrode layer 16 are not particularly limited, and it is preferable to select the optimum method and conditions according to the purpose.

[3.3. First oxide layer forming step]
Next, if necessary, the first oxide layer 18 is formed on the surface of the electrode layer 16 to obtain a laminated film (first oxide layer forming step). The first oxide layer 18 is formed by sputtering using a CZA target (A) having a predetermined composition in a reduced pressure oxygen atmosphere. The conditions for forming the first oxide layer 18 may be the same as or different from the conditions for forming the second oxide layer 14.
Here, the “laminated film” means a laminated film of electrode layer 16/first oxide layer 18, a laminated film of second oxide layer 14/electrode layer 16, or a second oxide layer 14/electrode layer 16. / Refers to a laminated film of the first oxide layer 18.
The other points regarding the first oxide layer forming step are the same as those of the second oxide layer forming step, and therefore the description thereof is omitted.

[3.4. Development step, etching step, and resist stripping step]
FIG. 2 shows a schematic diagram of the developing step, the etching step, and the resist stripping step.
First, after forming a laminated film including the second oxide layer 14/electrode layer 16/first oxide layer 18 on the surface of the substrate 12, as shown in FIG. 2A, the laminated film (first oxide layer) is formed. A photoresist film 20 is formed on the surface of the layer 18) and developed (developing step). The type of developer is not particularly limited. As the developing solution, an alkaline solution such as tetramethylammonium hydroxide (TMAH) is usually used.

Next, as shown in FIG. 2B, the photoresist film 20 is used as a mask to etch the stacked film of the second oxide layer 14/the electrode layer 16/the first oxide layer 18 (etching). Process). The etching method is not particularly limited, and an optimum method can be selected according to the purpose. Examples of the etching method include a dip method, a shower method, and a spray method.

Next, as shown in FIG. 2C, the photoresist film 20 is stripped (resist stripping step). The stripping of the photoresist film 20 is performed by immersing the substrate 12 in a stripping solution. The type of stripping solution is not particularly limited. As the stripping solution, an alkaline solution such as sodium hydroxide is usually used.

[4. Action]
When a Cu—Zn—A alloy (CZA) target containing Cu and Zn, and further containing an adhesion improving element A such as Mg or Al is used in a reduced pressure oxygen atmosphere, the substrate surface is sputtered. , Cu-Zn-A-based oxide film (CZA-O film) can be formed. The CZA-O film can be used as an antireflection film (oxide layer) of a touch panel or TFT. However, the CZA-O film thus obtained may be dissolved by an alkaline solution used during development or resist stripping, and the oxide layer may be discolored. The cause is the oxidation state of Cu in the CZA-O film. That is, if the proportion of Cu ₂ O present in the film increases, the resistance of the CZA-O film to the alkaline solution decreases.

On the other hand, when a Cu-Zn-A-based oxide film (CZA-O film) is formed by sputtering using a CZA target, the O ₂ fraction is relatively high and the N ₂ fraction is When the film formation is performed in a relatively low pressure oxidizing atmosphere, a CZA-O film having a large proportion of CuO (that is, a small proportion of Cu ₂ O) is obtained. An oxide film containing a large amount of CuO is difficult to dissolve in an alkaline solution. Therefore, when such a CZA-O film is used as an oxide layer, dissolution of the oxide layer at the time of development or peeling of the resist, and increase in reflectance and peeling of the electrode layer due to this can be suppressed. ..

(Examples 1 to 80, Comparative Examples 1 to 81)
[1. Preparation of sample]
As a target for forming the oxide layer, a Cu—Zn—A alloy (CZA) target containing Cu and Zn and, if necessary, the adhesion improving element A was used. However, in Comparative Example 41, a Cu target was used to form a Cu oxide film (Cu—O film) as the oxide layer. Further, a Cu target was used as a target for forming the electrode layer.

Using a sputtering device, on a glass substrate,
(A) CZA-O film or Cu-O film (thickness: 40 nm),
(B) Cu film (thickness: 170 nm), and
(C) CZA-O film or Cu-O film (thickness: 40 nm)
Were formed in this order. The pressure during film formation was 0.55 Pa in all cases.
Gas atmosphere during deposition of the CZA-O film or Cu-O film was an Ar-O ₂ atmosphere, O ₂ minutes rate was 15 to 100%. The gas atmosphere during the Cu film formation was an Ar atmosphere.

[2. Test method]
[2.1. CuO existence ratio]
The abundance ratio of CuO was measured using X-ray photoelectron spectroscopy (XPS). As the measuring device, Wuantera SXM manufactured by PHI was used. Monochromatic Al (1486.6 eV) was used as the X-ray source.
[2.2. Reflectance]
The reflectance was measured using a film thickness measuring device (Lambda Ace, manufactured by SCREEN).

[2.3. Corrosion test]
The sample was immersed in a 5% NaOH solution (liquid temperature: 25° C.) for 5 minutes, and the presence or absence of dissolution and the presence or absence of discoloration were visually confirmed. A sample having neither discoloration nor dissolution was evaluated as “◯”, a sample having no dissolution but discolored was evaluated as “Δ”, and a sample having both discoloration and dissolution was evaluated as “x”.

[3. result]
The results are shown in Tables 1 to 4. Note that Tables 1 to 4 also show the compositions of the targets used for forming the oxide layer. The following can be seen from Tables 1 to 4.

(1) In each of Comparative Examples 41 to 81, discoloration and dissolution of the CZA-O film or the Cu-O film on the outermost surface were observed. It is considered that this is because the proportion of CuO in the CZA-O film or the Cu-O film decreased because the O ₂ fraction during film formation was less than 20%.
(2) When the O ₂ fraction during film formation was increased to 30%, the CuO existing ratio was improved to 40% (Comparative Examples 1 to 40). As a result, the CZA-O film on the outermost surface was not dissolved, but discoloration was recognized.

(3) Further, when the O ₂ fraction during film formation was increased to 50% or more, the existence ratio of CuO was improved to 50% or more (Examples 1 to 80). As a result, not only the dissolution of the CZA-O film on the outermost surface but also discoloration was suppressed.
(4) The above effect was recognized regardless of the type and amount of the adhesion improving element A.
(5) In Comparative Example 41, the oxide layer is made of a Cu—O film, and thus the reflectance is high. On the other hand, the oxide layer containing Zn or the adhesion improving element A has a low reflectance.

(Example 81: Effect of gas partial pressure)
[1. Preparation of sample]
A CZA target made of 4 at% Zn-5 at% Al-Cu was used as a target for forming the oxide layer.

Using a sputtering device, on a glass substrate,
(A) CZA-O film (thickness: 40 nm),
(B) Cu film (thickness: 170 nm), and
(C) CZA-O film (thickness: 40 nm)
Were formed in this order. The pressure during film formation was 0.2 to 0.8 Pa.
Gas atmosphere during deposition of the CZA-O film was Ar-O ₂ atmosphere. Table 5 shows the gas partial pressure conditions and the input power during sputtering. The gas atmosphere during the Cu film formation was an Ar atmosphere.

[2. Test method]
[2.1. CuO existence ratio and composition ratio]
The abundance ratio and composition ratio of CuO were measured using X-ray photoelectron spectroscopy (XPS). As the measuring device, Wuantera SXM manufactured by PHI was used. Monochromatic Al (1486.6 eV) was used as the X-ray source.
[2.2. Corrosion test]
The sample was immersed in a 2% NaOH solution (liquid temperature: 40° C.) for 5 minutes, and the presence or absence of dissolution and the presence or absence of discoloration were visually confirmed.

[3. result]
FIG. 3 shows the relationship between the O ₂ fraction during film formation and the composition ratio of each element. FIG. 4 shows the relationship between the O ₂ fraction during film formation and the proportion of Cu compounds present. The following can be seen from FIGS. 3 and 4.

(1) Condition II has a high proportion of Cu ₂ O because the O ₂ fraction is 16.6%. As a result, the oxide layer was dissolved during the corrosion test.
(2) The condition VIII has a high proportion of CuO because the O ₂ fraction is 50%. As a result, discoloration and dissolution of the oxide layer were not observed during the corrosion test.
(3) It was recognized that the higher the O ₂ fraction during the formation of the oxide layer, the higher the proportion of CuO present.
(4) The effect of improving the alkali resistance by increasing the film forming pressure was not recognized, and the alkali resistance was improved by increasing the O ₂ fraction.

Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above embodiments and various modifications can be made without departing from the scope of the present invention.

The laminated film according to the present invention can be used as a touch panel used in bank ATMs, ticket vending machines, car navigation systems, PDAs, copiers, mobile phones, tablet PCs and the like.

Claims (8)

A laminated body having the following configuration.
(1) The laminated body is
Board,
An electrode layer formed on the substrate,
It comprises a first oxide layer formed on the surface of the electrode layer and/or a second oxide layer formed at the interface between the substrate and the electrode layer.
(2) The first oxide layer is
Including a first main element containing at least Cu and Zn,
The ratio of the amount of CuO present to the total amount of Cu compounds contained in the first oxide layer (the ratio of CuO present) is 45% or more.
(3) The first main element is
0.1≦Zn≦10.0 at%, and
0≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
And the balance consists of Cu and inevitable impurities.
(4) The second oxide layer is
Including a second main element containing at least Cu and Zn,
The ratio of the amount of CuO present to the total amount of Cu compounds contained in the second oxide layer (the ratio of CuO present) is 45% or more.
(5) The second main element is
0.1≦Zn≦10.0 at%, and
0≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
And the balance consists of Cu and inevitable impurities. The laminated body according to claim 1, wherein the existence ratio of CuO in the first oxide layer is 50% or more. The first main element is
0.1≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
The laminated body according to claim 1 or 2, which comprises: The layered product according to any one of claims 1 to 3, wherein an existence ratio of CuO in the second oxide layer is 50% or more. The second main element is
0.1≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
The laminated body according to any one of claims 1 to 4, which comprises: A method for manufacturing a laminate having the following configuration.
(1) The method for manufacturing the laminate is
An electrode layer forming step of forming an electrode layer on the substrate,
A first oxide layer is formed on the surface of the electrode layer to form a laminated film, and/or a second oxide layer is formed on the surface of the substrate before the electrode formation step. Forming a second oxide layer to obtain the laminated film;
A developing step of forming a photoresist film on the surface of the laminated film and developing it;
An etching step of etching the laminated film using the photoresist film as a mask,
And a resist stripping step of stripping the photoresist film.
(2) In the first oxide layer forming step,
0.1≦Zn≦10.0 at%, and
0≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
Using a Cu alloy target (A) containing
The first oxide layer is formed by sputtering in a reduced pressure oxidizing atmosphere having an O ₂ fraction of 35% or more and an N ₂ fraction of less than 1%.
(3) In the second oxide layer forming step,
0.1≦Zn≦10.0 at%, and
0≦B+Mg+Al+Ca+Ti+Cr+Mn+Ni+Sn≦10.0 at%
With a Cu alloy target (B) containing
The second oxide layer is formed by sputtering in a reduced pressure oxidizing atmosphere having an O ₂ fraction of 35% or more and an N ₂ fraction of less than 1%. The method for producing a laminate according to claim 6, wherein the O ₂ fraction in the first oxide layer forming step is 50% or more. The method for manufacturing a laminate according to claim 6, wherein the O ₂ fraction in the second oxide layer forming step is 50% or more.

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