JP2018170360A - Conductive film, electrode, electronic apparatus, electrostatic capacitance type input device, and manufacturing method of electrode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a conductive film with a structure of 2-3 layers, having a low resistance value required for an electrode of an electronic apparatus and an optical instrument and a low reflectivity of 10% or less; an electrode; an electronic apparatus; an electrostatic capacitance type input device; and a manufacturing method of an electrode.SOLUTION: There is provided a conductive film formed on a transparent substrate. The conductive film includes a metal layer and an oxynitride alloy layer laminated therein. The metal layer comprises an Al film or an Al alloy film formed on the transparent substrate. The oxynitride alloy layer is formed on the metal layer and formed of an Al alloy containing Al and at least one metal selected from the group consisting of Nd, Mn, Cu, Ti, Ta, Ge, La, and Zr, at least part of the oxynitride alloy layer being subjected to oxynitridization.SELECTED DRAWING: Figure 10

Description

  The present invention relates to a conductive film, an electrode, an electronic device, a capacitance-type input device, and a method for manufacturing an electrode that can be used for metal electrodes for electronic devices and optical devices.

  In recent years, in electrodes (including auxiliary electrodes that increase conductivity) used in various electronic devices using liquid crystal, organic EL, etc., especially large-sized touch sensors, which are input / output devices installed on the front surface of display elements, etc. Is progressing. Among the detection electrodes, wiring electrodes, and connection electrodes included in the touch sensor (panel), particularly in the detection electrodes, when the touch sensor is increased in size, the resistance component increases, and thus a lower resistance electrode has been required. .

Conventionally, the visibility of a display has been secured by using a highly transparent conductive metal oxide such as an oxide semiconductor mainly composed of In, Zn, Sn, Ti, or the like for an electrode for a touch panel. However, conductive metal oxides with high transparency have a limit in reducing the resistance value, and it is difficult to achieve the low resistance level required in recent years. Therefore, as an alternative material, there is a demand for practical use of a low resistance metal that can ensure visibility by micropatterning.
And in an electronic device in which a substrate with an electrode is arranged on the front surface of a display element such as a touch panel, it is a necessary condition that the visibility of display is not hindered. Therefore, the electrode can be shielded, scattered, stray light, reflected, etc. Only less is required.
However, if the conventional electrode made of a conductive metal oxide is simply replaced with metal, glare occurs due to the high reflectivity specific to the metal, and thus the reflectivity needs to be lowered. In addition, it is important to configure the conductor as low as possible and electrically connectable.

  Metals with low reflectivity include molybdenum (Mo), chromium (Cr), titanium (Ti), tantalum (Ta), tungsten (W) and their alloys, but these metals have a high resistance value. Applicable. On the other hand, silver (Ag), aluminum (Al), copper (Cu), etc. and their alloys have low resistance but high reflectance.

  A method of laminating a metal having a high resistance value and a low reflectance on a metal having a low resistance value and a high reflectance using the characteristics of these metals has been proposed. There are limits to the reduction.

For this reason, as a result of intensive studies, the present inventors have made MAM (Mo or Mo alloy / Al or Al alloy / Mo or Mo alloy three-layer structure compound) / In composite oxide / Mo alloy on a transparent substrate. By depositing six layers of In / In composite oxide, a conductive film having a low reflectance of about 3 to 8% in the visible light range of 400 to 700 nm was proposed (Patent Document 1).
According to this film, since it has a low reflectance, even when it is used as an electrode of a capacitive touch panel input device, glare is suppressed, a decrease in the contrast ratio of the display is suppressed, and transparent conductive Since the resistance value is small compared to the case of using a film, the power consumption of the capacitive input device can be reduced.

However, the conductive low reflection film of Patent Document 1 has a multilayer structure of six layers, and there are many types of metals and films used for film formation, and there has been a demand for improvement in film formation productivity and cost reduction. In addition, since the number of layers and film types are large, it is not suitable for film formation with an in-line sputtering apparatus.
Therefore, the transparent substrate includes a first layer made of an Al film or an Al alloy film, a second layer made of an Al—Cu alloy nitride film containing 10 to 13 at% Cu, and an oxide containing at least In and Zn. A conductive low-reflection film having a three-layer structure in which a third layer which is a transparent conductive film is formed has been proposed (Patent Document 2). Since the conductive low reflection film of Patent Document 2 has low reflectivity and conductivity, when used as an electrode in an input device such as a capacitive touch panel sensor, the chromaticity and reflectivity with the black matrix. The difference in (luminance) is small, and the electrodes are difficult to see.

However, according to the film of Patent Document 2, since the second layer contains Al and the third layer is an In-based film, the second layer Al—Cu alloy nitride film is used in the etching process after film formation. As a result, galvanic corrosion occurred due to the contact of moisture with the interface between the transparent conductive film made of the In-based oxide of the third layer, and the electrode of the capacitive input device was not suitable for practical use.
Galvanic corrosion is a corrosion phenomenon that occurs when different kinds of metal materials are brought into contact with each other in an aqueous electrolyte solution. Generally, the corrosion rate is lower than when the metal with the lower potential becomes the anode and is placed alone. Will increase. In the film of Patent Document 2, in the etching process, Al is in direct contact with In, which is a noble metal, for a long time in an aqueous electrolyte solution, so that an extreme battery is formed, and Al dissolves in the liquid and is ionized. To do.

  Therefore, a conductive low-reflection film having a two-layer structure using a combination of materials that hardly cause galvanic corrosion has been proposed (Patent Document 3). The conductive low reflection film of Patent Document 3 has a structure in which a transparent substrate is laminated with a first layer made of an Al film or an Al alloy film and a second layer made of a film in which a part of the Al alloy is nitrided. Thus, both low sheet resistance and low reflectance can be achieved.

Japanese Patent No. 5503651 JP 2016-31748 A Japanese Patent Laid-Open No. 2006-58055

However, according to the film of Patent Document 3, the resistance of the second layer nitride film, which is the surface layer, is low in resistance to warm pure water. There was a problem of collapse.
Nothing has been known that has a low reflectance and a low resistance value required for electrodes of touch panel type input devices, has a few layers and has a small number of layers, and can be used as an electrode of an electronic device or the like.

The present invention has been made in view of the above problems, and an object of the present invention includes a low resistance value required for an electrode of an electronic device or an optical device, and a low reflectance of 10% or less, An object of the present invention is to provide a method for producing a conductive film, electrode, electronic device, capacitance-type input device, and electrode having two to three layers.
Another object of the present invention is a conductive film, an electrode, an electronic device, a capacitance-type input device, and an electrode that are made of a low-resistance, low-reflectance film and can be manufactured by in-line sputtering without any trouble in the post-deposition process. It is in providing the manufacturing method of.

As a result of intensive studies by the present inventors to solve the above problems, a metal layer made of Al or an Al alloy film and an oxynitride alloy layer made of an oxynitrided Al alloy film are laminated on a transparent substrate. As a result, the inventors have found that a conductive film having low resistance, a low reflectance of about 10% or less in the visible light region, and good etching characteristics and resistance to hot pure water can be obtained, and the present invention has been achieved.
That is, the subject is a conductive film formed on a transparent substrate according to the conductive film of the present invention, the metal layer comprising an Al film or an Al alloy film formed on the transparent substrate, and the metal An Al alloy formed on the layer and containing Al and at least one metal selected from the group comprising Nd, Mn, Cu, Ti, Ta, Ge, La, Zr, and at least a portion thereof is oxynitrided This is solved by laminating the oxynitride alloy layer.

Thus, the transparent substrate, the metal layer made of Al film or Al alloy film, and the oxynitride alloy layer in which at least a part of the Al alloy is oxynitrided are laminated, so that the resistance is low and the reflectance is low. A conductive film having a low number of layers and good resistance to wet etching can be realized.
Since the resistance to hot pure water and wet etching processability are good, the reflectance characteristics are not significantly changed in the etching process after film formation as in the case of a conventional conductive film having no oxynitride alloy layer. It can be put to practical use as a metal electrode for optical equipment.
Furthermore, since the number of layers is two and less, it is possible to manufacture with in-line sputtering equipment, and the equipment occupancy can be increased compared to the case of using a carousel type sputtering equipment, etc. can do.
In addition, since Al is used in the metal layer and the oxynitride alloy layer, the optical characteristics are good, and the processing characteristics such as etching properties after the conductive film is formed are good.

At this time, in the oxynitride alloy layer, the atomic concentration ratio of nitrogen atoms to the total of nitrogen atoms and oxygen atoms in the region from the surface on the opposite side of the metal layer to the SiO ₂ equivalent depth of 20 nm is 20 at% or less. Also good.
Thus, since the atomic concentration ratio of nitrogen atoms to the total of nitrogen atoms and oxygen atoms in the surface layer of the conductive film is reduced to 20 at% or less, in the warm pure water cleaning step after film formation, the surface of the conductive film is It can melt | dissolve and it can suppress that a reflectance characteristic deteriorates.

Further, the reflectance at a wavelength of 410 to 670 nm of the transparent substrate on which the conductive film is formed may be 10% or less.
With this configuration, when used as a metal electrode of an electronic device such as a liquid crystal or an organic EL or an optical device, glare is suppressed and display visibility is prevented from being hindered.
The transparent substrate may be a plastic substrate, and the metal layer may be formed on an adhesion film formed on the plastic substrate.
Moreover, it consists of the said electrically conductive film, and may be used for an electronic device.
It is good also as an electronic device provided with the electrode which consists of the said electrically conductive film.

  In addition, according to the capacitance-type input device of the present invention, the problem is that the first electrode pattern extending in the first direction and the second direction different from the electrode pattern are formed on one surface of the transparent substrate. A capacitance-type input device for detecting capacitance, wherein at least one of the first electrode pattern and the second electrode pattern is on a transparent substrate. A metal layer made of an Al film or an Al alloy film formed on the metal layer, and formed on the metal layer, at least selected from the group comprising Al and Nd, Mn, Cu, Ti, Ta, Ge, La, Zr This is solved by being formed of a conductive film in which an Al alloy containing a kind of metal and an oxynitride alloy layer at least partially oxynitrided is laminated.

In addition, according to the method of manufacturing an electrode of the present invention, the above-described problem is a step of forming a metal layer made of Al or Al alloy on a transparent substrate by sputtering using an Al target or an Al alloy target, and Introducing oxygen gas and nitrogen gas using a target made of Al, Al, and an Al alloy containing at least one metal selected from the group including Nd, Mn, Cu, Ti, Ta, Ge, La, and Zr The Al alloy containing at least one kind of metal selected from the group including Al and Nd, Mn, Cu, Ti, Ta, Ge, La, Zr on the metal layer by sputtering, It is solved by including a step of forming a conductive film by laminating an oxynitride alloy layer that is oxynitrided and a step of cleaning the conductive film with pure water having a temperature higher than 40 ° C. .
Thus, on the metal layer, Al and an Al alloy containing at least one metal selected from the group comprising Nd, Mn, Cu, Ti, Ta, Ge, La, Zr, and at least partly And a process for forming a conductive film by laminating an oxynitride alloy layer in which oxynitridation is performed. Therefore, by oxynitriding the outermost layer of the conductive film, resistance to warm pure water after formation of the conductive film It is possible to suppress the deterioration of the reflectance characteristics even when immersed in warm pure water. In addition, since the Al alloy film is formed and oxygen and nitrogen are simultaneously supplied, the ratio of oxygen and nitrogen in the thickness direction of the oxynitride alloy layer can be relatively averaged. Furthermore, in the method of irradiating oxygen ions after forming a nitride alloy film or an alloy film, Al grows into abnormal particles and Al atoms and oxygen atoms do not mix homogeneously, but in the present invention, an Al alloy is formed. However, since oxygen and nitrogen are simultaneously supplied, oxygen atoms are mixed homogeneously into Al atoms.

According to the present invention, it is possible to provide a conductive film having a small number of layers and film types, good hot-pure water resistance and wet etching processability, low visibility, good visibility, and low resistance.
According to the present invention, electrical characteristics (conductivity), optical characteristics (refractive index and extinction coefficient), and etching characteristics (solubility in etchant, etching rate) can be freely controlled so as to have desired values. .

Therefore, electrical wiring connection to other metal wiring is easy, and while ensuring good electrical conductivity, it is possible to suppress glare caused by the metal layer by reducing the metal surface reflectance from the viewing side, and wet etching Thus, a conductive laminate capable of forming an arbitrary fine pattern at once can be achieved with a small number of layer structures.
When the conductive film comprising the laminate of the present invention is used as an electrode material for electronic equipment, the response speed can be improved, the visibility is improved by microfabrication and reflectance reduction, and the patterning is formed by collective etching. With the minimum layer structure, productivity can be improved and cost can be reduced.
By reducing the number of layers and film types, film formation with an in-line sputtering apparatus is facilitated, and productivity can be improved and costs can be reduced.

It is a schematic plane explanatory drawing which looked at the liquid crystal display panel of the touch sensor integrated display device concerning Embodiment 1 of the present invention from the visual recognition side. FIG. 3 is a schematic plan explanatory view of the arrangement of touch detection electrodes of the liquid crystal display panel of the touch sensor-integrated display device according to the first embodiment of the present invention. It is AA sectional drawing of FIG. It is a schematic perspective view of the input device carrying the electrostatic capacitance type input device which concerns on Embodiment 2 of this invention. It is a pattern diagram of the capacitance-type input device which concerns on Embodiment 2 of this invention. It is explanatory drawing which expanded partially the pattern figure of the electrostatic capacitance type input device which concerns on Embodiment 2 of this invention. It is a schematic sectional drawing equivalent to the BB line of FIG. 6 which concerns on Embodiment 2 of this invention. It is a graph which shows the measurement result of the reflectance in 400-700 nm of the glass substrate with a conductive film of Example 1 and Reference Example 1. It is a graph which shows the measurement result of the refractive index in 400-700 nm of the glass substrate with an electrically conductive film of Example 2, and an absorption coefficient. It is a graph which shows the result of the composition analysis of the oxynitride layer which is Examples 1-3 and the uppermost layer film of the contrast 1. It is a graph which shows the measurement result of the reflectance before immersion after immersion when the glass with a conductive film of Examples 1-3, comparative example 1, and reference example 1 is immersed in 40 degreeC warm pure water. It is a graph which shows the measurement result of the reflectance before immersion after immersion when the glass with an electrically conductive film of Examples 1-3, the comparative example 1, and the reference example 1 is immersed in 60 degreeC warm pure water. It is a graph which shows the measurement result of the reflectance before immersion after immersion when the glass with a conductive film of Examples 1-3, comparative example 1, and reference example 1 is immersed in warm pure water of 80 ° C. It is a SEM cross-sectional photograph of the sample which etched the electrically conductive film of Example 1. FIG. It is a SEM cross-sectional photograph of the sample which etched the electrically conductive film of the reference example 1. It is a table | surface which shows the result of the reliability evaluation test of Example 1, the reference example 1, and the electrically conductive film of the comparative examples 1-3. It is a graph which shows the result of having measured the reflectance before and behind warm pure water washing | cleaning about the comparative example 4 whose uppermost layer is a nitride alloy layer, and the test example 1 which formed the oxynitride layer on the nitride alloy layer.

Hereinafter, a conductive film, an electrode, an electronic device, a capacitive input device, and a method for manufacturing an electrode according to an embodiment of the present invention will be described with reference to FIGS.
The conductive film, electrode, electronic device, capacitive input device, and electrode manufacturing method of the present invention can be used for various electronic devices using liquid crystal, organic EL, etc., and electrodes of optical devices.
In this specification, a transparent conductive film has two properties of high electrical conductivity (specific resistance 1 × 10 ⁻³ Ω · cm or less) and transmittance of 80% or more in the visible light region (380 to 780 nm). In addition, Sn-doped In ₂ O ₃ (ITO), Zn-doped In ₂ O ₃ (IZO), and AZO are included.
In the present specification, “at%” is synonymous with “atomic%”.

<Embodiment 1>
In this embodiment, a capacitive touch input device with a touch panel will be described as an example of the electronic device.
The touch panel refers to a touch sensor integrated display device that is integrally provided with a touch sensor and a display device. As a touch panel, on the viewing side of a display device such as a liquid crystal device, a touch sensor substrate using a pattern formed of a transparent conductive film on a transparent substrate as a detection electrode is bonded, or on a display device substrate. There are some which form a touch sensor integrated pattern display device by forming a touch sensor electrode pattern.

In the touch panel, in order to detect a touch position with a finger or a touch pen, a row of electrodes in two directions orthogonal to the X direction and the Y direction is necessary. In the case of a capacitive touch sensor, there are types in which detection electrodes in two directions of X and Y are provided on the same surface as types provided on two different surfaces.
The electrostatic capacitance type is a form in which a position is detected by detecting a change in electrostatic capacitance between a fingertip and a detection electrode formed by patterning a conductive film.

In the type provided on two different surfaces, the liquid crystal driving common electrode provided as a plurality of stripe-shaped electrode patterns on the surface opposite to the viewing side of the color filter substrate of the liquid crystal display device is used as the sensor drive electrode, and the color filter substrate A touch detection device is configured from a touch detection electrode (in this case called a reception electrode) provided as an electrode pattern extending in a direction orthogonal to the extending direction of the electrode pattern of the drive electrode on the surface on the viewing side of X and Y detection electrodes in two directions are provided on two different surfaces.
With this configuration, in the touch detection device, when the drive electrode driver applies a drive signal to the drive electrode, a touch detection signal is output from the touch detection electrode, and touch detection is performed.

On the other hand, in the type provided on the same surface, the detection electrodes in one of the X and Y directions (one drive electrode and the other receive electrode) are arranged on the same layer on the viewing side of the transparent substrate of the color filter substrate. Configure. A plurality of columns along the X-axis direction are arranged intermittently in the Y-axis direction orthogonal to each other, and each of the plurality of columns along the Y-axis direction is a first light-transmitting electrode. A second translucent electrode disposed between the rows and between the columns, wherein the first translucent electrode and the second translucent electrode are insulated from each other by a transparent insulating film; At the intersection of the first and second translucent electrodes, the second translucent electrode has its own pattern continuously conducting, and each of the first translucent electrodes has the first translucent electrode. The X and Y detection electrodes in two directions are provided on the same surface by being electrically connected to each other by a plurality of jumpers made of a conductive material through a contact hole of a transparent insulating film on the photoelectrode. The
In any of the two types provided on the same surface and the type provided on the same surface, the detection electrode can be constituted by a transparent electrode formed of a transparent conductive film in order to prevent a decrease in transmittance on the color filter substrate.

Hereinafter, the capacitive input device according to the first embodiment will be described as a type provided on the former two different surfaces. The latter type provided on the same surface will be described as a second embodiment.
The capacitive input device according to the present embodiment is an input device of the touch sensor integrated display device 1 integrally including a touch sensor and a display device, and uses the conductive film of the present embodiment as a touch detection electrode. Is.
The touch sensor integrated display device 1 includes, for example, a capacitive liquid crystal display panel P1 shown in FIGS.
As shown in FIG. 1, the liquid crystal display panel P1 of the present embodiment is formed of a substantially rectangular plate-like body, and has a predetermined width from the end along the entire periphery of the liquid crystal display panel P1 when viewed from the viewing side. The decoration part 2 formed in frame shape in the area | region of this and the substantially rectangular operation part 3 formed in the inside of the decoration part 2 are formed.

  As shown in FIGS. 2 and 3, the operation unit 3 is formed with a touch detection electrode 15 mainly extending in the X direction and made of the conductive film of the present embodiment, and is used as a drive electrode extending in the Y direction. The touch can be detected by using the capacitance between the touch detection electrode 15 and the touch detection electrode 15. Here, the liquid crystal driving common electrode 25 that scans and operates the liquid crystal is used as the driving electrode of the sensor. This embodiment is a two-layer type in which the touch detection electrode 15 and the common electrode 25 as a drive electrode are formed on different surfaces. In the liquid crystal display panel P1 of the present embodiment, a common electrode 25 as a drive electrode is formed on the TFT substrate 20 so as to extend in the Y direction, and the color filter substrate and the black matrix are formed on the same surface. 10, a touch detection electrode 15 made of the conductive film of the present embodiment extending mainly in the X direction is formed. In principle, the conductive film constituting the touch detection electrode 15 may be only in the X direction, but is also required in the Y direction for touch detection with a thin object other than a finger.

As shown in FIG. 3, the liquid crystal display panel P <b> 1 of the present embodiment is formed by bonding a color filter substrate 10 and a TFT substrate 20 in a state where a liquid crystal 30 is sealed.
On the surface of the color filter substrate 10 on the liquid crystal 30 side that is the non-viewing side of the glass substrate 11, as shown in FIGS. 2 and 3, a grid-like black matrix 12 and a black matrix 12 are arranged. A color filter 13 is laminated.
The color filter 13 is configured by periodically arranging, for example, three color filter layers of red (R), green (G), and blue (B), and each display pixel includes R, G, and B. The colors are associated as a set. 2 and 3, a rectangle indicated by symbol 13 indicates one of R, G, and B in the display pixel. The rectangular pattern made of the conductive film is arranged to include a plurality of display pixels.

In this embodiment, the color filter substrate 10 in which the black matrix 12 and the color filter 13 are formed on the same substrate is used. However, instead of the color filter substrate 10, a black matrix substrate having only the black matrix 12 is used. It may be used. In this case, the color filter layer is provided on another substrate different from the black matrix substrate.
An alignment film 16 is further formed on the surface of the color filter substrate 10 on the liquid crystal 30 side.

As shown in FIGS. 2 and 3, the touch detection electrode 15 made of the conductive film of the present embodiment is formed on the operation unit 3 on the opposite side of the liquid crystal 30 of the color filter substrate 10. The wiring pattern 50 and the connection terminal 50a formed integrally with the decoration portion 2 are electrically connected. The wiring pattern 50 and the connection terminal 50a are also formed of the conductive film of the present embodiment integrally with the touch detection electrode 15, but may be formed of other metal wirings or the like.
The conductive film constituting the touch detection electrode 15, the wiring pattern 50, and the connection terminal 50a is a metal layer made of an Al film or an Al alloy film formed on a transparent substrate, laminated on the metal layer, Al, Al and an Al alloy containing at least one metal selected from the group including Nd, Mn, Cu, Ti, Ta, Ge, La, Zr, and an oxynitride alloy layer partially oxynitrided; Are stacked.
The conductive film of the present embodiment is directly formed on the transparent glass substrate 11, but is not limited to this, and is formed on an adhesion layer made of a dielectric film formed on the substrate. A conductive film may be formed. In particular, since the plastic substrate has weak adhesion to Al or Al alloy, the conductive film of this embodiment may be formed on the adhesion layer formed on the plastic substrate.

The metal layer is made of an Al film or an Al alloy film.
By using the Al film or the Al alloy film as the wiring metal, wet etching processability with a phosphorous acetate acetic acid-based etchant is improved. Here, the phosphoric acid acetate etching solution means a mixed solution containing at least phosphoric acid, nitric acid and acetic acid.

  Specifically, it is preferable to use the above Al film or Al alloy film in which the electric resistivity of the metal layer single film is 20 μΩ · cm or less. The electrical resistivity of the metal layer is sufficiently lower than that of an oxynitride alloy layer with an electrical resistivity of 1 kΩ / cm or less, so the charge flow is dominated by the metal layer and the sheet resistance of the laminated structure Is also reduced.

The Al alloy film is an Al alloy film containing at least one element selected from the group consisting of Nd, Cu, Ti, Mn, Ta, Ge, La, Zr, and Ni.
As an alloy component of the Al alloy film, at least one of a refractory metal element and a rare earth metal element may be contained. Thereby, the thermal aggregation inhibitory effect is exhibited. Here, the refractory metal element means a metal having a melting point of 1200 ° C. or higher, such as Mo, Ti, Ta, W, Cr, and Mn. The rare earth metal element means a lanthanoid element, that is, 15 elements from La to Lu, and scandium and yttrium. Among these, the heat resistance is enhanced by using an Al alloy containing a high melting point metal element such as Ti, Ta, and Mn, and further, the corrosion resistance against corrosion by halogen, salt water, etc. existing depending on the use environment is improved. It is also preferable to contain an element having a noble electrode potential with respect to Al, such as Cu, Ge, Zr, or Ni, as an alloy component. Thereby, for example, when a structure in which an Al alloy electrode and a transparent electrode are in contact with each other is used, the battery reaction at the connection interface between the Al alloy thin film and the transparent electrode can be suppressed, and electrolytic corrosion can be suppressed.

  The alloy element content of the Al alloy film of the metal layer is such that the lower limit of the alloy element content is higher than the refractory metal element, rare earth metal element, and Al in order to ensure the heat resistance and corrosion resistance described above. It is preferable to contain at least one element among the elements having electric potential in a total amount of 0.1 at% or more, more preferably 0.2 at% or more.

On the other hand, the upper limit of the alloy element content is preferably as follows in order to realize low sheet resistance. That is, when the rare earth metal element and the refractory metal element are contained, the upper limit of the total content of the rare earth metal element and the upper limit of the total content of the refractory metal element are each 2 at% or less. It is more preferable that each be 1 at% or less. When an element having an electrode potential nobler than that of Al is contained, the upper limit of the total content of the elements is preferably 3 at% or less, and more preferably 2 at% or less.
The total content of the refractory metal element, the rare earth metal element, and the element having an electrode potential more noble than Al is preferably 3 at% or less, more preferably 2 at% or less.

  The film thickness of the metal layer is preferably 50 nm or more in order to lower the sheet resistance value when it has a laminated structure to a predetermined range. When the thickness of the metal layer is less than 50 nm, it is difficult to obtain a desired sheet resistance value. More preferably, it is 100 nm or more. However, if the thickness of the metal layer exceeds 400 nm, wet etching processability and manufacturability with a phosphorous acetate acetic acid-based etchant may be reduced. Therefore, the thickness of the metal layer is preferably 400 nm or less.

  The oxynitride alloy layer is an Al alloy including Al and at least one metal selected from the group including Nd, Mn, Cu, Ti, Ta, Ge, La, and Zr, and at least a part thereof is oxynitrided. It is a layer. The alloy of the oxynitride alloy layer is preferably composed of an Al alloy containing at least one element selected from the group consisting of Mn and Cu from the viewpoint of improving corrosion resistance against halogen, salt water, and the like.

  The oxynitride alloy layer preferably has an absorption coefficient of 0.3 or more at a wavelength of 450 nm, a wavelength of 550 nm, and a wavelength of 650 nm. The oxynitride alloy layer preferably has a refractive index of 1.0 or more at a wavelength of 450 nm, a wavelength of 550 nm, and a wavelength of 650 nm. By using a layer having a high absorption coefficient and a high refractive index as the oxynitride alloy layer, the reflectance of the entire conductive film can be reduced.

  In this specification, “at least a part is oxynitrided” means that the Al alloy contains at least a nitrogen atom and an oxygen atom so that a desired effect is effectively exhibited. The oxynitride that satisfies the stoichiometric composition need not be used. However, “at least part” includes at least the surface layer of the oxynitride alloy layer in order to improve the warm pure water characteristics.

In the oxynitride alloy layer of this embodiment, the atomic concentration ratio of nitrogen atoms to the total of nitrogen atoms and oxygen atoms is 10 to 24 at%. In particular, in the region from the surface opposite to the metal layer of the oxynitride alloy layer to 20 nm, the atomic concentration ratio of nitrogen atoms to the total of nitrogen atoms and oxygen atoms is 10 to 20 at%. In the region from the surface on the opposite side of the metal layer of the oxynitride alloy layer to 10 nm, the atomic concentration ratio of nitrogen atoms to the total of nitrogen atoms and oxygen atoms is 10 to 19 at%.
Thus, in the outermost surface layer region from the surface on the opposite side of the metal layer of the oxynitride alloy layer to 10 nm, the atomic concentration ratio of nitrogen atoms to the total of nitrogen atoms and oxygen atoms is 20 at% or less, thereby making galvanic The resistance to warm pure water can be improved by preventing the occurrence of corrosion. As a result, the wet etching processability after forming the conductive film on the transparent substrate can be improved.

  The preferable doping amount of metal elements other than Al contained in the metal oxynitride alloy layer varies depending on the type of element. The Nd doping amount is suitably about 0.1 at% or more and 3 at% or less.

<Method for producing electrode>
Hereinafter, the manufacturing method of the electrode in one embodiment of the present invention is explained.
The conductive film of this embodiment is formed by a sputtering method. A batch type sputtering apparatus may be used, or an inline sputtering apparatus having at least two film forming chambers is used, and a metal layer forming process is performed in the first film forming chamber, and then the second film forming process is continuously performed. An oxynitride alloy layer forming step may be performed in the film chamber.
First, a transparent substrate and a target for a metal layer are set in a sputtering apparatus, and a metal layer film forming step is performed in which a metal layer is formed by sputtering on the transparent substrate.
As the target, an Al target or an alloy target of Al and at least one element selected from the group consisting of Nd, Cu, Ti, Mn, Ta, Ge, La, Zr and Ni is used.
This step is performed under the following conditions.
-Substrate temperature: Room temperature to 400 ° C
Atmosphere gas: Ar Gas Ultimate vacuum: 1~10 × 10- ⁴ Pa
・ Sputtering power: 5-6W / cm ²
・ Film thickness: 300 ~ 400nm
When the transparent substrate is a plastic substrate, an adhesion layer forming step for forming an adhesion layer on the plastic substrate is performed before the metal layer deposition step. In the metal layer deposition step, the adhesion layer is formed on the adhesion layer. A metal layer is formed.

Next, the transparent substrate on which the metal layer was formed in the metal layer forming step and the target for the oxynitride alloy layer were set in the sputtering apparatus, and the mixed gas of oxygen and nitrogen was introduced while the oxynitride alloy layer was formed. An oxynitride alloy layer forming step for sputtering is performed. The oxynitride alloy layer forming step corresponds to a step of forming a conductive film by laminating the oxynitride alloy layers recited in the claims.
In this step, a target made of Al and an Al alloy containing at least one metal selected from the group consisting of Nd, Mn, Cu, Ti, Ta, Ge, La, and Zr is used as the target.
This step is performed under the following conditions.
-Substrate temperature: Room temperature to 400 ° C
-Atmospheric gas: Ar gas, nitrogen gas, oxygen gas, oxygen gas flow rate / nitrogen gas flow rate: 5-20%
・ Achieving vacuum: 1-10 × 10 ^-4 Pa
・ Sputtering power: ^{2 to 3} W / cm ²
・ Film thickness: 10-100nm

Thus, by simultaneously introducing three types of gases, Ar gas, nitrogen gas and oxygen gas, during sputtering, the Al alloy is oxynitrided almost uniformly over the entire length in the thickness direction of the oxynitride alloy layer. be able to.
In the method of oxidizing the surface of the film by irradiating oxygen ions after forming the alloy film, Al grows into abnormal particles, and the Al alloy and oxygen atoms do not mix. In the method of irradiating oxygen ions, an ion irradiation apparatus is required in the sputtering apparatus or separately from the sputtering apparatus. On the other hand, in this step, since the oxynitrogen mixed gas is introduced, the oxynitrogen atoms can be introduced almost uniformly into the Al alloy, and the number of manufacturing steps can be reduced.

After performing the above metal layer forming step and oxynitride alloy layer forming step to form a conductive film, electrode patterning is performed.
In the electrode pattern formation, first, the surface of the conductive film is leveled (cleaned), and a resist coating process is performed in which a photoresist is coated by a spin coater or spraying.
Thereafter, using the patterned mask original, an exposure (baking) step of baking the pattern by irradiating ultraviolet rays is performed.
Next, an uncured photoresist is removed, and a developing process for developing the pattern of the original plate is performed.
Thereafter, an etching process is performed to remove unnecessary portions from which the photoresist has been removed by etching.
A patterning process of the electrode is completed by performing a stripping process for stripping the photoresist and a cleaning process for immersing in hot pure water for cleaning.

  In the present embodiment, at least one metal selected from the group including Al and Nd, Mn, Cu, Ti, Ta, Ge, La, Zr on the metal layer made of an Al film or an Al alloy film. An oxynitride alloy layer comprising at least a part of which is oxynitrided is laminated, but instead of the oxynitride alloy layer, Mo— You may comprise as a laminated body which laminated | stacked the nitride Mo-Nb alloy layer which consists of a nitride film of Nb alloy, and an IGO (indium gallium oxide) layer. With this configuration, galvanic corrosion is unlikely to occur in the etching process after film formation, and both low sheet resistance and low reflectivity are achieved, and a conductive low-reflection film with a small number of three layers is achieved. can do.

Conventionally, using a combination of materials that are unlikely to cause galvanic corrosion, a transparent substrate is laminated with a first layer made of an Al film or an Al alloy film and a second layer made of a film in which a part of the Al alloy is nitrided 2 A conductive low-reflection film having a layer structure has been proposed (Japanese Patent Laid-Open No. 2006-58055). According to this film, the second layer nitride film, which is the surface layer, has low resistance to hot pure water, and the photolithographic process is difficult to flow.
Therefore, protection of the second layer is necessary, but since the second layer contains Al, when an indium oxide-based film is formed on the second layer, the second layer Al and the third layer indium oxide Directly contacted and caused galvanic corrosion.
Therefore, in Reference Example 1, an indium oxide film can be formed on the third layer by using a Mo—Nb alloy instead of the second layer Al alloy. Thereby, galvanic corrosion is suppressed, it has sufficient hot pure water tolerance, and it can be set as the low reflective electrically conductive film with the favorable film formability which can perform the process of a photolithograph suitably. Moreover, the low reflective conductive film of Reference Example 1 obtained can also achieve low sheet resistance and low reflectance.

Further, instead of the IGO layer, a transparent conductive film layer made of another indium-based transparent conductive oxide such as an ITO (indium tin oxide) layer or an IZO (indium zinc oxide) layer may be formed.
Since IGO has etching characteristics close to those of Mo and Al, it can be suitably used in Reference Example 2. Conventionally, among indium-based transparent conductive oxides, a process for forming a low-reflection film using IGO has been established and has been widely used. Therefore, conventional etching conditions and the like can be used by using IGO.

Hereinafter, a conductive film in which a metal layer made of an Al film or an Al alloy film, a nitrided Mo—Nb alloy layer, and an IGO layer is formed on a substrate will be described. However, the description of the same configuration as in Embodiment 1 is omitted.
The Nb ratio in the nitrided Mo—Nb alloy layer is 20 at% or less, and more preferably, Nb is 10 at%.
The film thickness of the nitrided Mo—Nb alloy layer is 30 nm or more, preferably 40 nm or more, and 60 nm or less, preferably 50 nm or less.

The IGO layer preferably has an absorption coefficient of 0.01 or more at wavelengths of 450 nm, 550 nm, and 650 nm, and preferably has a refractive index of 1.9 or more at wavelengths of 450 nm, 550 nm, and 650 nm.
The thickness of the IGO layer is 20 nm or more, preferably 30 nm or more, and 60 nm or less, preferably 50 nm or less.

In the electrode manufacturing method in which an electrode is manufactured by forming a metal layer made of an Al film or an Al alloy film, a nitrided Mo—Nb alloy layer, or an IGO layer on a substrate, first, as in the first embodiment, the metal layer is formed. Perform the process.
After that, set the transparent substrate on which the metal layer was deposited in the metal layer deposition process and the target for the nitrided Mo-Nb alloy layer in the sputtering device, and introduce the nitrogen gas while introducing the nitrided Mo-Nb alloy layer. A Mo—Nb alloy layer film forming step for sputtering film formation is performed.
In this step, a target made of a Mo—Nb alloy is used as the target.
This step is performed under the following conditions.
-Substrate temperature: 25 ° C (room temperature)
Atmosphere gas: Ar gas, nitrogen gas, ultimate vacuum: 1.13 × 10- ⁴ Pa
・ Sputtering power: 1.5W / cm ²
・ Film thickness: 40nm

After that, set the transparent substrate on which the metal layer and the nitrided Mo-Nb alloy layer were formed on the sputtering device and the target for the IGO layer, and introduce the IGO layer by sputtering while introducing the oxygen gas. A film process is performed.
In this step, a target made of an In—Ga alloy is used as the target.
This step is performed under the following conditions.
-Substrate temperature: 25 ° C (room temperature)
Atmosphere gas: Ar gas, oxygen gas, ultimate vacuum: 1.13 × 10- ⁴ Pa
・ Sputtering power: 2.5W / cm ²
・ Film thickness: 30nm
After performing the above metal layer forming step, nitrided Mo—Nb alloy layer forming step, and IGO layer forming step to form a conductive film, electrode patterns are formed by the same procedure as in the first embodiment. .

<Embodiment 2>
The conductive film, electrode, electronic device, and method for manufacturing the conductive film of the present invention can also be applied to the capacitive input device 101 of the touch panel of FIGS. 4 to 7 as an electronic device. The capacitive input device 101 according to the present embodiment is a type in which detection electrodes in two directions of X and Y are provided on the same surface.
The capacitive input device 101 according to the present embodiment is used as the input device 100 by being configured in combination with the image display device 102 as shown in FIG. The input device 100 includes at least a capacitive input device 101, an image display device 102, and a flexible flat cable 103. In the input device 100, the capacitive input device 101 is disposed so as to overlap the viewing side of the image display device 102, that is, the side operated by the user, and the operator inputs the surface of the capacitive input device 101. An input unit 101a for performing an input operation and an output unit 101b for outputting a signal from the input unit 101a to the outside are provided.

  And the flexible flat cable 103 for outputting the input signal is connected to the output part 101b of the capacitive input device 101. The flexible flat cable 103 is connected to a detection drive circuit (not shown).

The image display device 102 mounted on the input device 100 can use a general liquid crystal panel, an organic EL panel, or the like, and displays a moving image or a still image.
The input device 100 employs a capacitance method that determines the position operated by the user by measuring the ratio of the current amount. The operation will be described below.

  The input device 100 includes a capacitance type input device 101, and a user visually recognizes an image displayed on the image display device 102 via the transparent capacitance type input device 101. Then, while viewing the image displayed on the image display device 102, the capacitive input device 101 is touched with a finger or a stylus pen to input information. At this time, since the finger and the stylus pen are conductors, they have capacitance between the detection electrodes (the first electrode pattern 120 and the second electrode pattern 130) of the capacitive input device 101. As a result, the electrostatic capacitance at the position touched with the finger or the stylus pen is reduced, and the lowered position is calculated by a detection drive circuit (not shown) so that the position can be detected.

  FIG. 5 is an enlarged view of a part of the capacitive input device 101. As shown in FIG. 4, the capacitance-type input device 101 includes an input unit 101a and an output unit 101b. As shown in FIG. 5, the input unit 101a is formed on the transparent substrate 104, and is formed by forming a first electrode pattern 120 extending in the X-axis direction and a second electrode pattern 130 extending in the Y-axis direction. The output unit 101b is formed by forming wiring patterns 150 and 160 and connection terminals 150a and 160a electrically connected to the wiring patterns 150 and 160. The wiring patterns 150 and 160 are connected to the connection terminals 150a and 160a on the opposite side. The end portions are electrically connected to the electrode patterns 120 and 130. The connection terminals 150a and 160a are connected to the flexible flat cable 103.

  As shown in FIG. 6, a substantially rhombic first transparent conductive film 121a and a second transparent conductive film 131a made of a transparent conductive film are formed on the first electrode pattern 120 and the second electrode pattern 130, respectively. Yes. The first transparent conductive films 121a adjacent in the X direction are continuously formed by the connection portions 131c at the apexes of the approximately rhombus, and as a result, the second electrode pattern 130 continuous in the Y axis direction is formed. The second transparent conductive film 131a adjacent in the Y direction has a pair of opposing vertices connected by a connection part 131c made of a transparent conductive film to form a second electrode pattern 130 continuous in the Y-axis direction.

  6 is a partially enlarged explanatory view of the pattern diagram of the capacitive input device 101 according to the first embodiment, and FIG. 7 is a schematic cross-sectional view corresponding to the line AA in FIG.

  As shown in FIGS. 6 and 7, most of the first transparent conductive film 121a is covered with the insulating film 121b, and the portion of the first transparent conductive film 121a that faces the connecting portion 131c has the insulating film 121b. The first transparent conductive film 121a is exposed from the insulating film 121b at the contact portion 152a at the position of the contact hole 122. The second transparent conductive film 131a is also covered with the insulating film 131b. The connection part 131c that connects the adjacent second transparent conductive films 131a is covered with the insulating film 141a on all surfaces other than the surface in contact with the transparent substrate 104. An insulating film (not shown) is also formed below the wiring patterns 150 and 160, and the entire area on the transparent substrate 104 other than the contact holes 122 is covered with the insulating film.

As shown in FIG. 7, a narrow strip-shaped conductive member 151a is provided between a pair of opposing contact portions 152a so as to cross the connection portion 131c perpendicularly and bridge over the insulating film 141a. Adjacent first transparent conductive films 121a are electrically connected in the X direction.
As shown in FIG. 7, the capacitive input device 101 has an upper surface covered with a protective film 171.

In the present embodiment, the wiring patterns 150 and 160, the connection terminals 150a and 160a, and the conductive member 151a are composed of electrodes made of the same conductive film as in the first embodiment.
Since the structure of the conductive film and the electrode is the same as that of Embodiment Mode 1, description thereof is omitted.

  Hereinafter, the present invention will be described in more detail based on specific examples. However, the present invention is not limited to the following embodiments.

<Test 1>
The conductive films (Examples 1 to 3) according to Examples of the present invention and the conductive films according to Comparative Examples (Reference Example 1, Comparative Examples 1 to 3) were formed, and the characteristics of the conductive films were compared. Hereinafter, each example, a reference example, and comparison will be described.
Preparation of conductive film First, conductive films of Examples 1 to 3 and Reference Example 1 and Comparative Examples 1 to 3 were prepared according to the following procedure.

(Examples 1-3: Al—Nd layer (330 nm) / AlN nitride alloy layer (60 nm))
On the glass substrate, an Al—Nd alloy layer having a thickness of 330 nm and an oxynitride layer of an Al alloy having a thickness of 60 nm were prepared by the following procedure, and were used as the conductive films of Examples 1 to 3, respectively. In Examples 1 to 3, the ratio of oxygen gas to nitrogen gas in the introduced gas at the time of forming the oxynitride layer of the Al alloy was changed.
That is, an Al—Nd alloy layer having a thickness of 330 nm was formed on a glass substrate by the DC magnetron sputtering method using a carousel-type batch type sputtering apparatus and a cryopump under the following film formation conditions.
-Target: 14 mm thick Al-Nd target-Ultimate vacuum: 1.13 x 10 ^-4 Pa
-Substrate temperature: 25 ° C (room temperature)
・ Sputtering power: 5.5W / cm ²
・ Film thickness Ai-Nd: 330nm
・ Ar flow rate: 500sccm

Subsequently, the target, film thickness, sputtering power and introduced gas were changed as follows, and three types of Al alloy oxynitride layers having different ratios of oxidation and nitridation were formed on the Al—Nd alloy layer. Al-Cu-Nd was used as the Al alloy.
・ Target: 6mm thickness Al-Cu-Nd alloy (Al 89.6at%, Cu 7.0at%, Nd 3.4at%) target ・ Sputtering power: 2.5W / cm ²
・ Film thickness: 60nm
・ Ar flow rate: 650sccm
・ N ₂ flow rate: 88sccm
O ₂ flow rate: 5 sccm (Example 1), 10 sccm (Example 2), 15 sccm (Example 3)
Thus, the conductive films of Examples 1 to 3 were obtained.

(Comparative 1: Al-Nd layer (330 nm) / Al nitride layer (60 nm))
An Al—Nd alloy layer having a thickness of 330 nm and an Al alloy nitride layer having a thickness of 60 nm were formed on a glass substrate by the following procedure to obtain a conductive film having a proportionality of 1.
That is, an Al—Nd alloy layer having a thickness of 330 nm was formed on a glass substrate by a DC magnetron sputtering method using the same apparatus as in Examples 1 to 3 under the same conditions.

Next, an Al alloy nitride layer was formed on the Al—Nd alloy layer by changing the target, film thickness, sputtering power and introduced gas as follows.
・ Target: 6mm thickness Al-Cu-Nd alloy target ・ Sputtering power: 2.5W / cm ²
・ Film thickness: 60nm
・ Ar flow rate: 650sccm
・ N ₂ flow rate: 88sccm
As a result, a conductive film having a proportionality of 1 was obtained.

(Reference Example 1: Al—Nd (330 nm) / Mo—Nb nitride (40 nm) / IGO (30 nm))
An Al—Nd alloy layer with a thickness of 330 nm, a nitride layer of Mo—Nb alloy with a thickness of 40 nm, and an IGO layer with a thickness of 30 nm were formed on a glass substrate by the following procedure, and used as the conductive film of Reference Example 1. .
That is, an Al—Nd alloy layer having a thickness of 330 nm was formed on a glass substrate by a DC magnetron sputtering method using the same apparatus as in Examples 1 to 3 under the same conditions.

Next, the target, film thickness, sputtering power, and introduced gas were changed as follows to form a Mo—Nb alloy nitride layer on the Al—Nd alloy layer.
・ Target: Thickness 9mmMo-Nb target ・ Sputtering power: 1.5W / cm ²
・ Film thickness: 40nm
・ Ar flow rate: 500sccm
・ N ₂ flow rate: 88sccm

Subsequently, the IGO layer was formed on the nitride layer of the Mo—Nb alloy by changing the target, film thickness, sputtering power and introduced gas as follows.
・ Target: IGO 6t 5 ”x 62” target ・ Sputtering power: 2.5W / cm ²
・ Film thickness: 30nm
・ Ar flow rate: 500sccm
・ O ₂ flow rate: 12sccm
Thus, the conductive film of Reference Example 1 was obtained.

(Comparison 2: Mo-Nb / Al-Nd / Mo-Nb / ITO (40 nm) / Mo-Nb (10 nm) / ITO (40 nm))
On the glass substrate, Mo-Nb (10 nm) / Al-Nd (330 nm) is formed by sequentially depositing a 10-nm thick Mo-Nb layer, a 330-nm thick Al-Nd alloy layer, and a 40-nm thick ITO layer. ) / Mo—Nb (30 nm) / ITO (40 nm) / Mo—Nb (10 nm) / ITO (40 nm) were prepared by the following procedure to obtain a conductive film having a comparative 2 ratio.
That is, first, a 10-nm-thick Mo—Nb layer was formed on a glass substrate by the DC magnetron sputtering method using the same apparatus as in Examples 1 to 3 under the following film formation conditions.
・ Target: Thickness 9mmMo-Nb target ・ Sputtering power: 1.5W / cm ²
・ Film thickness: 10nm
・ Ar flow rate: 100sccm

Next, an Al—Nd alloy layer having a thickness of 330 nm was formed on the Mo—Nb alloy layer by changing the target, film thickness, sputtering power, and introduced gas as follows.
・ Target: 14mm thickness target ・ Sputtering power: 5.5W / cm ²
・ Film thickness: 330nm
・ Ar flow rate: 500sccm
Thereafter, a Mo—Nb layer having a thickness of 10 nm was formed in the same manner as the Mo—Nb layer formed first on the glass substrate.

Next, the target, film thickness, sputtering power and introduced gas were changed as follows, and a 40 nm ITO layer was formed on the Mo-Nb layer.
・ Target: ITO 6t 5 ”x 62” target ・ Sputtering power: 2.5W / cm ²
・ Film thickness: 40nm
・ Ar flow rate: 500sccm
・ O ₂ flow rate: 12sccm

Furthermore, a 10 nm thick Mo—Nb layer and a 40 nm ITO layer were formed under the same conditions as those already formed.
As a result, a conductive film having a proportional 2 was obtained.

(Comparison 3: Mo-Nb / Al-Nd / Mo-Nb / IGO (40 nm) / Mo-Nb (10 nm) / IGO (40 nm))
A Mo-Nb (10 nm) / Al-Nd (330 nm) film is formed by sequentially depositing a 10 nm thick Mo-Nb layer, a 330 nm thick Al-Nd alloy layer, and a 40 nm thick IGO layer on a glass substrate. ) / Mo-Nb (30 nm) / ITO (40 nm) / Mo-Nb (10 nm) / ITO (40 nm) were prepared by the following procedure to obtain a conductive film of comparative 3.
That is, first, a 10-nm-thick Mo—Nb layer was formed on a glass substrate by the DC magnetron sputtering method using the same apparatus as in Examples 1 to 3 under the following film formation conditions.
・ Target: Thickness 9mmMo-Nb target ・ Sputtering power: 1.5W / cm ²
・ Film thickness: 10nm
・ Ar flow rate: 100sccm

Next, an Al—Nd alloy layer having a thickness of 330 nm was formed on the Mo—Nb alloy layer by changing the target, film thickness, sputtering power, and introduced gas as follows.
・ Target: 14mm thickness target ・ Sputtering power: 5.5W / cm ²
・ Film thickness: 330nm
・ Ar flow rate: 500sccm
Thereafter, a Mo—Nb layer having a thickness of 10 nm was formed in the same manner as the Mo—Nb layer formed first on the glass substrate.

Next, the target, film thickness, sputtering power, and introduced gas were changed as follows, and a 40 nm IGO layer was formed on the Mo-Nb layer.
・ Target: IGO 6t 5 ”x 62” target ・ Sputtering power: 2.5W / cm ²
・ Film thickness: 40nm
・ Ar flow rate: 500sccm
・ O ₂ flow rate: 12sccm

Further, a Mo—Nb layer having a thickness of 10 nm and an IGO layer having a thickness of 40 nm were formed under the same conditions as those already formed.
As described above, a conductive film having a proportionality 3 was obtained.

O Characteristics of conductive films The characteristics of the conductive films of Examples 1 to 3, Reference Example 1 and Comparative Examples 1 to 3 formed as described above were measured.
-Resistance value and reflectance of the conductive film of Example 1 and Reference Example 1 About the conductive film of Example 1 and Reference Example 1, using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), the wavelength from 400 nm to 700 nm. The reflectance in the visible light range was measured. Moreover, the resistance value was measured using a resistivity meter (Mitsubishi Chemical Lorester GP), and the reflectance was measured using a film thickness meter (ULVAC DEKTAKXT). The reflectance measurement results are shown in FIG. 8, and the resistance value and film thickness measurement results are shown in Table 1.

-Glass / Al alloy optical constants The glass as the transparent substrate used in Examples 1 to 3, Reference Example 1 and Comparative Examples 1 to 3 was subjected to the same conditions as in Example 2, that is, the oxygen gas introduction amount was 10 sccm. A layer (60 nm) was formed, and an optical constant in a visible light region of 400 to 700 nm was measured using a spectroscopic ellipsometer (M-220 manufactured by JASCO Corporation). The results are shown in FIG.
・ Composition analysis of Al oxynitride alloy layer Using Examples 1 to 3 and Comparative 1 oxynitride Al alloy layer by XPS (X-ray Photoelectron Spectroscopy) using a photoelectron spectrometer (JPS-9000MC manufactured by JEOL Ltd.) A compositional analysis was performed. In the measurement by the spectroscopic device, Ar ions were used as incident ions.
The results are shown in FIG. The horizontal axis represents the SiO ₂ equivalent depth from the surface of the oxynitride Al alloy layer.
In the conductive film of Example 1, the concentration ratio of nitrogen atoms was 10.6 to 22.9 at%, and the concentration ratio of oxygen atoms was 77.1 to 89.4 at%. In the conductive film of Example 2, the concentration ratio of nitrogen atoms was 12.1 to 22.3 at%, and the concentration ratio of oxygen atoms was 77.7 to 87.9 at%. In the conductive film of Example 3, the concentration ratio of nitrogen atoms was 12.1 to 23.7 at%, and the concentration ratio of oxygen atoms was 76.3 to 87.9 at%.

As described above, in the conductive film of the proportional 1, there were portions where the concentration ratio of nitrogen atoms exceeded 30 at% depending on the SiO ₂ conversion depth, whereas in the conductive films of Examples 1 to 3, The atomic concentration ratio was less than 24 at% at all SiO ₂ conversion depths.
In the conductive film of the comparative 1, there were portions where the oxygen atom concentration ratio was less than 70 at% depending on the SiO ₂ conversion depth, whereas in the conductive films of Examples 1 to 3, the oxygen atom concentration was The ratio was 76 at% or more at all SiO ₂ conversion depths.

・ Warm pure water immersion test The conductive films of Examples 1 to 3, Comparative Example 1 and Reference Example 1 were immersed in warm pure water at 40 ° C., 60 ° C., and 80 ° C. for 20 minutes. The reflectance in the visible light region was measured. The reflectance was measured using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.).
The results when immersed in warm pure water at 40 ° C., 60 ° C., and 80 ° C. for 20 minutes are shown in FIGS.
From the result of FIG. 11, when immersed in warm pure water at 40 ° C. for 20 minutes, no change was observed in the reflectance before and after immersion in any conductive film.
However, as shown in FIGS. 12 and 13, when immersed in warm pure water at 60 ° C. and 80 ° C. for 20 minutes, the reflectivity after immersion changes greatly in the conductive film of Comparative Example 1 compared to before immersion. Was.
From hot pure water immersion test results of the composition analysis results and FIGS. 11 to 13 in FIG. 10, in all of the terms of SiO ₂ depth, the concentration ratio of nitrogen atoms, not more than 30 at%, in all the terms of SiO ₂ depth, It was found that when the oxygen atom concentration ratio was 70 at% or higher, the reflectance characteristics were substantially unchanged before and after immersion even when immersed in warm pure water at 40 ° C. to 80 ° C.

Etching evaluation The conductive film of Example 1 and Reference Example 1 was subjected to etching evaluation.
The conductive film of Example 1 and Reference Example 1 was coated with a photoresist (OFPR-800LB manufactured by Tokyo Ohka Kagaku Co., Ltd.), and a patterned mask original plate was used to irradiate ultraviolet rays to bak the pattern onto the photoresist. Using a developer (TMAH (tetramethylammonium hydroxide) aqueous solution), the uncured photoresist is removed to develop the pattern of the original, and unnecessary portions of the conductive film from which the photoresist has been removed are etched into the etching solution. It was removed by etching using (phosphoric acid, nitric acid, acetic acid mixed solution). Thereafter, the photoresist remaining on the conductive film was peeled off and washed to obtain etching samples of Example 1 and Reference Example 1.
Thereafter, SEM cross-section analysis (JEOL JSM-6700F) was performed on the etching samples of Example 1 and Reference Example 1.
SEM cross-sectional photographs of the etching samples of Example 1 and Reference Example 1 are shown in FIGS. As shown in FIGS. 14 and 15, in Reference Example 1, no clear boundary was observed in the photograph of the etched surface, and it was found that the etched surface was uneven, whereas in Example 1, the etched surface was It was observed as a clear boundary and it was found that good etching was performed.

-Reliability evaluation The following reliability evaluation was performed about the electrically conductive film of Example 1, Reference example 1, and Comparative Examples 1-3.
A moisture resistance test was performed in which each conductive film was held at 60 ° C. and 90% for 24 hours. In the moisture resistance test, the resistance value before the test and after the 24-hour holding test under the condition of 90% at 60 ° C. is measured, and {(the resistance value after the test−the resistance value before the test) / the measured value before the test} × 100 (%) The rate of change in resistance value was calculated from the equation. Further, the appearance of each conductive film after being kept at 60 ° C. and 90% for 24 hours was visually evaluated, and the case of film peeling was evaluated as “x”, the case of surface change as Δ, and the case of no change as “good”.
The results of the test are shown in FIG. As shown in FIG. 16, all the conductive films had an appearance of “◯”, and the resistance change rates were all within ± 2.0%, and any of the conductive films had no problem with moisture resistance.

In addition, a chemical resistance test was performed by immersing in a developer at 30 ° C. (TMAH (tetramethylammonium hydroxide) 2.38% solution) for 2 minutes. In the chemical resistance test, the resistance value before the test and after the immersion test is measured, and the change rate of the resistance value is calculated by the formula {(resistance value after test−resistance value before test) / measured value before test} × 100 (%). did. Further, the appearance of each conductive film after the immersion test was visually evaluated, and the case of film peeling was evaluated as x, the case of surface change as Δ, and the case of no change as ◯.
As a result, as shown in FIG. 16, the conductive film of Example 1 and Comparative Example 3 was good in appearance and the conductive film of Reference Example 1 was Δ, while the conductive films of Comparative Examples 1 and 2 were X. In the conductive film of Example 1 and Comparative Example 4, the change rate of the resistance value was also within an allowable range within ± 15%, but the change rate of the resistance value of the conductive film of Reference Example 1, Comparative Example 1 and 2 Was over ± 20%. In particular, it was found that the chemical resistance with respect to the developing solutions of the proportions 1 and 2 is not sufficient for practical use.

An etching time measurement test was conducted until an unnecessary portion of the conductive film not covered with the photoresist was removed with an etching solution (mixed acid composed of phosphoric acid, nitric acid, and acetic acid) at 40 ° C.
According to the user product standard, the etching time is specified to be 95 seconds or less, and as a result, as shown in FIG. 16, it is 87 seconds or less for all the conductive films. The level was met.
In addition, a test for confirming the presence or absence of an etching residue that remains without being etched when immersed in an etching solution at 40 ° C. (mixed acid composed of phosphoric acid, nitric acid, and acetic acid mixed solution) for 95 seconds was performed. The presence or absence of the etching residue after immersion was visually confirmed, and the case where the film was not completely dissolved was evaluated as x, the case where the film remained in a dotted pattern was evaluated as Δ, and the case where the film was completely dissolved was evaluated as ◯.
As a result, as shown in FIG. 16, all the conductive films were evaluated as “good”, and in the 95-second immersion test specified by the standard, no etching residue remained and the standard was satisfied.

A chemical resistance test was conducted by immersing in a resist stripper (Nagase Resist N-342) at 40 ° C for 95 seconds. The presence or absence of film surface abnormality after immersion in the resist stripper was visually confirmed, and the film peeling was evaluated as x, the surface change was evaluated as Δ, and the case without change was evaluated as ◯.
As a result, as shown in FIG. 16, the evaluation was “good” for all the conductive films, and no film surface abnormality was observed. It was confirmed that the resist remover had sufficient chemical resistance against immersion for 95 seconds.

In accordance with JIS standards, a film adhesion strength confirmation test was performed by a cross-cut tape peeling test. In the test, a light collector (manufactured by Cabin Kogyo Co., Ltd., apparatus name: PROCABN 67-Z) was used, and the case of film peeling was evaluated as x, the case of partial film peeling was evaluated as △, and the case of no film peeling was evaluated as ◯.
As a result, as shown in FIG. 16, the evaluation was “good” for all the conductive films, and it was confirmed that the films had sufficient film adhesion strength.

  From the above reliability evaluation test, the conductive films of the comparative examples 1 and 2 have insufficient resistance to the developing solution and are not suitable for practical use, whereas the conductive films of Example 1, the comparative example 1 and the reference example 1 Was found to have sufficient properties for practical use in all the items of moisture resistance, chemical resistance to developer / resist stripper, presence of etching residue, film adhesion strength, and film hardness.

<Test 2>
In this test, an oxynitride film of an Al alloy is formed on the nitride film of the Al alloy, and a test is performed to check whether the change in spectral characteristics after cleaning with hot pure water, which is a problem with the Al alloy nitride film, is improved Went.
A conductive film according to a test example of the present invention (Test example 1) and a conductive film according to a comparative example (comparative 4) were formed, and changes in spectral characteristics before and after cleaning were examined.
Preparation of conductive film First, the conductive film of Test Example 1 and Comparative Example 4 was prepared by the following procedure.

(Test Example 1: AlNd 1 wt% / Al alloy (Cu, Nd) Nx / Al alloy (Cu, Nd) NOx)
On a glass substrate, an Al—Nd alloy layer (Nd 1 wt%) having a thickness of 320 nm, an oxynitride layer of an Al alloy (Cu, Nd) having a thickness of 40 nm, Examples 1 to 3, Reference Example 1, and Comparative Examples 1 to 3 Thus, the conductive film of Test Example 1 was prepared.
At this time, an Al-Nd alloy target and an Al alloy (Cu, Nd) target (Al 89.6 at%, Cu 7.0 at%, Nd 3.4 at%) are used as targets, and the acid of the Al alloy (Cu, Nd) is used. The amounts of Ar gas, nitrogen gas, and oxygen gas introduced during the formation of the nitride layer were 500 sccm, 88 sccm, and 10 sccm, respectively.
The conductive film of Test Example 1 was prepared on three glass substrates in the same sputtering apparatus, and the resistance values, film thicknesses, and average values of the three conductive films were as shown in Table 2.

(Comparison 4: AlNd1wt% / Al alloy (Cu, Nd) Nx)
A conductive film similar to Test Example 1 was produced except that the uppermost Al alloy (Cu, Nd) oxynitride layer was not provided, and a conductive film having a proportionality 4 was obtained. That is, a 320 nm thick Al—Nd alloy layer (Nd 1 wt%) and a 40 nm thick Al alloy (Cu, Nd) nitride layer on a glass substrate were used in Examples 1 to 3, Reference Example 1 and 3 was produced in accordance with the procedure of No. 3, and a conductive film with a proportionality of 4 was obtained.

A cleaning test is performed in which the glass substrate with conductive film 4 in comparison with Test Example 1 is immersed in warm pure water at 60 ° C. for 1 hour. Was used to measure the reflectance in the visible light range from 400 nm to 700 nm.
The results are shown in FIG.
When the reflectance change rate before and after cleaning is an absolute value of {(reflectance after cleaning−reflectivity before cleaning) / reflectivity before cleaning} × 100 (%), from the graph of FIG. Before and after cleaning, the reflectance change rate was a maximum of 138% (wavelength 636 nm), whereas in Test Example 1, the maximum reflectance change rate was 5.5% (wavelength 540 nm). It was.
From the results of this test example, it was found that the resistance to warm pure water is improved by forming an alloy oxynitride film on the surface of the alloy nitride film.

P1 Liquid crystal display panel 1 Touch sensor integrated display device 2 Decoration unit 3 Operation unit 10 Color filter substrate 11, 21 Glass substrate 12 Black matrix 13 Color filter 15 Touch detection electrode 15L Lower touch detection electrodes 16, 26 Alignment films 17, 27 Adhesive layer 18, 28 Polarizing plate 19, 121b, 131b, 141a Insulating film 20 TFT substrate 15U Drive electrode 25 Common electrode 30 Liquid crystal 31 Spacer 50, 60 Wiring pattern 50a, 150a, 160a Connection terminal 100 Input device 101 Capacitive input Device 101a Input unit 101b Output unit 102 Image display device 103 Flexible flat cable 104 Transparent substrate 120 First electrode pattern 121a First transparent conductive film 122 Contact hole 130 Second electrode pattern 131a Second transparent conductive film 131c Connection unit 15 0, 160 Wiring pattern 151a Conductive member 171 Protective film

Claims (8)

A conductive film formed on a transparent substrate,
A metal layer made of an Al film or an Al alloy film formed on the transparent substrate;
An Al alloy formed on the metal layer and including Al and at least one metal selected from the group including Nd, Mn, Cu, Ti, Ta, Ge, La, and Zr, at least a part of which is an acid A conductive film characterized by being laminated with a nitrided oxynitride alloy layer. In the oxynitride alloy layer, the atomic concentration ratio of nitrogen atoms to the total of nitrogen atoms and oxygen atoms in a region from the surface on the opposite side of the metal layer to a SiO ₂ equivalent depth of 20 nm is 20 at% or less. The conductive film according to claim 1.   The conductive film according to claim 1 or 2, wherein the transparent substrate on which the conductive film is formed has a reflectance of 10% or less at a wavelength of 410 to 670 nm. The transparent substrate is a plastic substrate;
The conductive film according to claim 1, wherein the metal layer is formed on an adhesion film formed on the plastic substrate.   An electrode comprising the conductive film according to claim 1 and used in an electronic device.   An electronic device comprising an electrode comprising the conductive film according to claim 1. On one surface of the transparent substrate, a first electrode pattern extending in a first direction and a second electrode pattern extending in a second direction different from the electrode pattern are provided, and a static electricity detecting capacitance is detected. A capacitive input device,
At least one of the first electrode pattern and the second electrode pattern is
A metal layer made of an Al film or an Al alloy film formed on a transparent substrate;
An Al alloy formed on the metal layer and including Al and at least one metal selected from the group including Nd, Mn, Cu, Ti, Ta, Ge, La, and Zr, at least a part of which is an acid A capacitance-type input device comprising a conductive film formed by laminating a nitrided oxynitride alloy layer. A step of forming a metal layer made of Al or Al alloy on a transparent substrate by sputtering using an Al target or an Al alloy target,
By sputtering using oxygen gas and nitrogen gas, using a target made of Al and an Al alloy containing at least one metal selected from the group including Nd, Mn, Cu, Ti, Ta, Ge, La, and Zr. An Al alloy containing Al and at least one metal selected from the group comprising Nd, Mn, Cu, Ti, Ta, Ge, La, and Zr on the metal layer, at least a portion of which is oxynitrided Laminating the formed oxynitride alloy layer, and forming a conductive film;
And a step of cleaning the conductive film with pure water having a temperature higher than 40 ° C.