JP2022064724A - Metal layer, touch sensor, dimmer element, photoelectric conversion element, hot-wire control member, antenna, electromagnetic wave shield member, image display apparatus, and method for producing metal layer - Google Patents

Abstract

To provide a metal layer having high thermostability; a touch sensor, dimmer element, photoelectric conversion element, hot-wire control member, antenna, electromagnetic wave shield member, and image display apparatus, each of which includes the metal layer; and a method for producing a metal layer having high thermostability.SOLUTION: A metal layer 1 includes, as a main component, a metal belonging to period 3 and/or period 4, and also includes a krypton atom and/or a xenon atom.SELECTED DRAWING: Figure 1

Description

The present invention relates to a metal layer, a touch sensor, a dimming element, a photoelectric conversion element, a heat ray control member, an antenna, an electromagnetic wave shielding member, an image display device, and a method for manufacturing the metal layer. A touch sensor, a dimming element having the metal layer, a photoelectric conversion element having the metal layer, a heat ray control member having the metal layer, an antenna having the metal layer, an electromagnetic wave shielding member having the metal layer, and the metal layer. The present invention relates to an image display device provided and a method for manufacturing a metal layer.

In recent years, it is known that a metal layer is used as an electrode member of a touch panel or the like.

As such a metal layer, for example, a conductive metal layer formed by sputtering in the presence of argon gas has been proposed (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2012-234996

On the other hand, when the metal layer is processed into an electrode member, the metal layer may be heated. In such a case, it is required to suppress an increase in the resistance value of the metal layer (excellent in heating stability) before and after heating.

The present invention relates to a metal layer having excellent heating stability, a touch sensor having the metal layer, a dimming element having the metal layer, a photoelectric conversion element having the metal layer, a heat ray control member having the metal layer, and the metal layer. It is an object of the present invention to provide an antenna including the above, an electromagnetic wave shielding member including the metal layer thereof, an image display device including the metal layer thereof, and a method for manufacturing the metal layer having excellent heating stability.

The present invention [1] is a metal layer containing a metal belonging to the 3rd period and / or the 4th period as a main component, and also containing a krypton atom and / or a xenon atom.

The present invention [2] includes the metal layer according to the above [1], which has conductivity.

The present invention [3] includes the metal layer according to the above [1] or [2], which has a pattern shape.

The present invention [4] includes a touch sensor including the metal layer according to any one of the above [1] to [3].

The present invention [5] includes a dimming element including the metal layer according to any one of the above [1] to [3].

The present invention [6] includes a photoelectric conversion element including the metal layer according to any one of the above [1] to [3].

The present invention [7] includes a heat ray control member including the metal layer according to any one of the above [1] to [3].

The present invention [8] includes an antenna including the metal layer according to any one of the above [1] to [3].

The present invention [9] includes an electromagnetic wave shielding member including the metal layer according to any one of the above [1] to [3].

The present invention [10] includes an image display device including the metal layer according to any one of the above [1] to [3].

The present invention [11] is a method for producing a metal layer in which a metal layer is formed by a sputtering method targeting a metal belonging to the 3rd period and / or the 4th period in the presence of krypton and / or xenon.

In the method for producing a metal layer of the present invention, a metal layer is formed by a sputtering method targeting a metal belonging to the 3rd period and / or the 4th period in the presence of krypton and / or xenon.

When the metal layer is formed by the sputtering method, atoms derived from the sputtering gas are incorporated into the metal layer.

In this method, since krypton and / or xenon having a larger atomic weight than argon is used as the sputtering gas instead of argon, atoms derived from the sputtering gas (krypton atom and / or xenon atom) are incorporated into the metal layer. Can be suppressed.

This makes it possible to manufacture a metal layer having excellent heating stability.

Therefore, the metal layer of the present invention is excellent in heating stability.

Further, since the metal layer, the touch sensor, the dimming element, the photoelectric conversion element, the heat ray control member, the antenna, the electromagnetic wave shielding member, and the image display device of the present invention include the metal layer of the present invention, they are excellent in heating stability.

FIG. 1 is a schematic view showing an embodiment of the metal layer of the present invention. FIG. 2 is a schematic view showing an embodiment of the method for producing a metal layer of the present invention, FIG. 2A shows a step of preparing a base material, and FIG. 2B shows the presence of a sputtering gas (krypton and / or xenon). Below, a step of forming (arranging) a metal layer on one surface in the thickness direction of a base material by a sputtering method targeting a metal belonging to the third cycle and / or the fourth cycle is shown. FIG. 3 is a schematic view showing an aspect in which the metal layer of the laminate shown in FIG. 2B is patterned.

As shown in FIG. 1, the metal layer 1 has a film shape (including a sheet shape) having a predetermined thickness, extends in a plane direction orthogonal to the thickness direction, and has a flat upper surface and a flat lower surface.

The metal layer 1 contains a metal and an atom derived from a trace amount of sputtering gas, and preferably comprises a metal and an atom derived from the sputtering gas. Specifically, the metal layer 1 contains a metal as a main component and an atom derived from a sputtering gas as a trace component, and is preferably composed of a metal and an atom derived from the sputtering gas. More specifically, in the metal layer 1, atoms derived from a trace amount of sputtering gas are present in the metal matrix.

The metal contains, as a main component, a metal belonging to the 3rd period and / or the 4th period. That is, the metal layer 1 contains a metal belonging to the third period and / or the fourth period as a main component.

Examples of the metal belonging to the third period include magnesium (Mg), aluminum (Al), silicon (Si), phosphorus (P) and the like, and aluminum (Al) is preferable.

Examples of the metal belonging to the 4th period include titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn). , Gallium (Ga) and the like, preferably copper (Cu) and the like.

Metals belonging to the 3rd cycle and / or the 4th cycle can be used alone or in combination of two or more.

The metal may also contain other metals as subcomponents.

Examples of other metals include metals belonging to the 5th period and metals belonging to the 6th period.

Examples of the metal belonging to the 5th period include zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and indium (In). And so on.

Examples of the metal belonging to the 6th period include tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au) and the like.

Other metals can be used alone or in combination of two or more.

The metal preferably does not contain other metals and consists of a metal belonging to the 3rd and / or 4th period, more preferably a metal belonging to the 3rd period or a metal belonging to the 4th period. Consists of.

The atom derived from the sputtering gas will be described in detail later, but is an atom incorporated into the metal layer 1 when the metal layer 1 is formed by the sputtering method, and as an atom derived from the sputtering gas, specifically, Examples include krypton and / or xenon atoms. That is, the metal layer 1 contains krypton atoms and / or xenon atoms.

As the atom derived from the sputtering gas, a krypton atom or a xenon atom is preferable, and a krypton atom is more preferable.

The content of atoms derived from the sputtering gas in the metal layer 1 is, for example, 0.5 atomic% or less, preferably 0.2 atomic% or less, more preferably 0.1 atomic% or less, still more preferably. , 0.05 atomic% or less, particularly preferably 0.02 atomic% or less, particularly preferably 0.01 atomic% or less. The content of atoms derived from the sputtering gas is identified, for example, by fluorescent X-ray analysis or Rutherford Backscattering Spectrum (abbreviated as RBS), which will be described later with reference to Examples.

The lower limit of the content is the corresponding ratio when the presence of krypton atom and / or xenon atom can be confirmed by a fluorescent X-ray analyzer or Rutherford backscatter analysis, and is at least 0.00001 atom% or more. ..

The thickness of the metal layer 1 is, for example, 10 nm or more, preferably 30 nm or more, and for example, 5000 nm or less, preferably 1500 nm or less, more preferably 500 nm or less, still more preferably 300 nm or less, particularly preferably. , 100 nm or less.

The method for measuring the thickness of the metal layer 1 will be described in detail in Examples described later.

Next, a method for manufacturing the metal layer 1 will be described with reference to FIG.

In this production method, in the presence of a sputtering gas (krypton and / or xenon), the metal is subjected to a sputtering method targeting the above-mentioned metal (a metal containing a metal belonging to the 3rd cycle and / or the 4th cycle as a main component). Form layer 1.

To form the metal layer 1 by the sputtering method, first, the base material 2 is prepared as shown in FIG. 2A.

The base material 2 has a film shape.

Examples of the base material 2 include a polymer film from the viewpoint of flexibility. Examples of the material of the polymer film include olefin resins such as polyethylene, polypropylene, and cycloolefin polymers, for example, polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, and (meta) such as polymethacrylate. ) Acrylic resin (acrylic resin and / or methacrylic resin), for example, polycarbonate resin, polyether sulphon resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, polystyrene resin and the like, preferably polyester. Resin, more preferably polyethylene terephthalate (PET) can be mentioned.

The thickness of the base material 2 is, for example, 1 μm or more, preferably 10 μm or more, preferably 30 μm or more, and for example, 300 μm or less, preferably 200 μm or less, more preferably 100 μm or less, still more preferably. It is 60 μm or less.

The thickness of the base material 2 can be measured using a dial gauge (manufactured by PEACOCK, "DG-205").

Further, if necessary, the base material 2 can be subjected to a surface treatment such as a hard coat treatment from the viewpoint of imparting scratch resistance.

Next, as shown in FIG. 2B, the metal layer 1 is formed (arranged) on one surface in the thickness direction of the base material 2 by a sputtering method targeting the metal in the presence of a sputtering gas (krypton and / or xenon). do.

Specifically, in the sputtering apparatus, while transporting the base material 2 along the peripheral surface of the film forming roll and facing the target made of the metal with one surface in the thickness direction of the base material 2, the sputtering gas (preferably). Sputters in the presence of krypton or xenon, more preferably krypton).

Examples of the sputtering include a bipolar sputtering method, an ECR (electron cyclotron resonance) sputtering method, a magnetron sputtering method, and an ion beam sputtering method.

Further, in sputtering, in addition to krypton and / or xenon, a reactive gas such as oxygen can be present.

The partial pressure of krypton and / or xenon in the sputtering apparatus is, for example, 0.01 Pa or more, preferably 0.1 Pa or more, more preferably 0.3 Pa or more, and for example, 10 Pa or less, preferably 10 Pa or more. It is 5 Pa or less, more preferably 1 Pa or less.

The pressure (deposition pressure) in the sputtering apparatus is the total pressure of the partial pressure of krypton and / or xenon and the partial pressure of the reactive gas, and is, for example, 0.1 Pa or more, preferably 0.3 Pa or more. Also, for example, it is 15 Pa or less, preferably 10 Pa or less, more preferably 5 Pa or less, still more preferably 1 Pa or less, and particularly preferably 0.5 Pa or less.

Examples of the power source used for sputtering include a direct current (DC) power source, an alternating current medium frequency (AC / MF) power source, a high frequency (RF) power source, and a high frequency power source on which a direct current power source is superimposed, and a direct current (DC) power source is preferable. ) Power supply is mentioned.

The strength of the horizontal magnetic field on the target surface is, for example, 10 mT or more, preferably 20 mT or more, and for example, 200 mT or less, preferably 100 mT or less. By adjusting the strength of the horizontal magnetic field on the target surface to the above range, the atomic content of the sputtering gas in the metal layer 1 can be adjusted.

The temperature of the film forming roll is, for example, −30 ° C. or higher, preferably −10 ° C. or higher, and for example, 180 ° C. or lower, preferably 90 ° C. or lower, more preferably 60 ° C. or lower, still more preferably. , 40 ° C or lower, particularly preferably less than 10 ° C.

By the above sputtering, the metal layer 1 is formed (arranged) on one surface of the base material 2 in the thickness direction. As a result, the metal layer 1 is obtained, and the laminated body 3 in which the base material 2 and the metal layer 1 are sequentially provided toward one side in the thickness direction is obtained.

And such a metal layer 1 has conductivity.

When the metal layer 1 has conductivity, it can be suitably used as an electrode member provided in a touch sensor, a dimming element, a photoelectric conversion element, a heat ray control member, an antenna, an electromagnetic wave shielding member, an image display device, etc., which will be described later. can.

Specifically, the surface resistance value of the metal layer 1 is, for example, 5Ω / □ or less, preferably 0.5Ω / □ or less, more preferably 0.35Ω / □ when the metal is made of copper (Cu). Below, it is more preferably 0.30 Ω / □ or less, more preferably 0.23 Ω / □ or less, and usually 0.001 Ω / □ or more, and 0.01 Ω / □ or more, preferably 0.01 Ω / □ or more. It is 0.1Ω / □ or more.

When the metal is made of aluminum (Al), the surface resistance value of the metal layer 1 is, for example, 10 Ω / □ or less, preferably 5.00 Ω / □ or less, and more preferably 2.00 Ω / □ or less. It is more preferably 1.70 Ω / □ or less, and usually exceeds 0.001 Ω / □, and is 0.1 Ω / □ or more, preferably 1.00 Ω / □ or more.

The surface resistance value can be measured by the 4-terminal method in accordance with JIS K7194.

When the metal is made of copper (Cu), the resistivity of the metal layer 1 is, for example, 10 × 10 ^-6 Ω · cm or less, preferably 2.50 × 10 ^-6 Ω · cm or less. It is preferably 2.40 × 10 ^-6 Ω · cm or less, more preferably 2.30 × 10 ^-6 Ω · cm or less, and particularly preferably 2.05 × 10 ^-6 Ω · cm or less, and also. For example, 0.10 × 10 ^-6 Ω · cm or more.

When the metal is made of aluminum (Al), the resistivity of the metal layer 1 is, for example, 20 × 10 ^-6 Ω · cm or less, preferably 9.0 × 10 ^-6 Ω · cm or less. It is preferably 7.0 × 10 ^-6 Ω · cm or less, and is, for example, 0.10 × 10 ^-6 Ω · cm or more, preferably 1.0 × 10 ^-6 Ω · cm or more.

The resistivity can be calculated based on the following equation (1) using the surface resistivity value obtained by the 4-terminal method and the thickness of the metal layer 1 in accordance with JIS K7194.

Specific resistance of metal layer 1 = thickness of metal layer 1 x surface resistance value of metal layer 1 (1)
Further, when the metal layer 1 is manufactured by the above sputtering method, atoms derived from the sputtering gas are incorporated into the metal layer 1.

However, in this method, since krypton and / or xenon having a larger atomic weight than argon is used as the sputtering gas instead of the commonly used argon, it is possible to suppress the incorporation of atoms derived from the sputtering gas into the metal layer 1. ..

That is, although such a metal layer 1 contains a krypton atom and / or a xenon atom, as described above, the amount of the krypton atom and / or the xenon atom incorporated is suppressed, so that the metal layer 1 is suppressed. Can suppress an increase in the resistance value before and after heating (in other words, this metal layer 1 is excellent in heating stability).

Further, such a metal layer 1 is excellent in heating stability as described above, while containing a metal belonging to the 3rd cycle and / or the 4th cycle as a main component. That is, according to this method, the metal layer 1 having excellent heating stability can be manufactured without using an expensive metal such as gold (Au) (a metal belonging to the 6th period) as a main component. Therefore, it is excellent in industrial productivity.

The metal layer 1 may be provided with a resin layer (not shown) adjacent to the metal layer 1 on the side opposite to the base material 2. The resin layer is, for example, an adhesive layer or an adhesive layer for adhering the metal layer 1 to another member, and is, for example, a coat layer for protecting the metal layer 1. The material of the resin layer is not limited, and a known resin such as an acrylic resin can be used. Further, the resin layer may contain an ultraviolet absorber or a corrosion inhibitor. The material of the ultraviolet absorber and the corrosion inhibitor is not limited, and examples thereof include benzotriazole compounds disclosed in Japanese Patent Application Laid-Open No. 2015-0222397.

Further, as shown in FIG. 3, the metal layer 1 can be patterned in the laminated body 3. That is, the metal layer 1 has a pattern shape.

To pattern the metal layer 1, for example, the metal layer 1 is etched. As a result, the laminated body 3 has a pattern portion 4 having the metal layer 1 and a non-pattern portion 5 having no metal layer 1. The laminated body 3 may be provided with a resin layer (not shown) on the upper surfaces of the pattern portion 4 and the non-pattern portion 5. The resin layer is, for example, an adhesive layer or an adhesive layer for bonding the laminated body 3 and another member, and is, for example, a coat layer that protects the pattern portion 4 of the laminated body 3. Further, the resin layer may contain an ultraviolet absorber, a corrosion inhibitor, and a migration inhibitor, and may contain, for example, a benzotriazole-based compound disclosed in JP-A-2015-0222397.

The metal layer 1 is used for various purposes, for example, a touch sensor, a dimming element (voltage-driven dimming element such as PDLC, PNLC or SPD, current-driven dimming such as electrochromic (EC)). Elements), photoelectric conversion elements (solar cell elements typified by organic thin-film solar cells and dye-sensitized solar cells), heat ray control members (near-infrared reflection and / or absorption members, far-infrared reflection and / or absorption members) , An antenna (light transmissive antenna), an electromagnetic wave shielding member, a heater member, an electrode member provided in an image display device and the like.

Since such a touch sensor, a dimming element, a photoelectric conversion element, a heat ray control member, an antenna, an electromagnetic wave shielding member, a heater member, and an image display device include the metal layer 1 of the present invention, they are excellent in heating stability.

Specific numerical values such as the compounding ratio (content ratio), physical property values, parameters, etc. used in the following description are the compounding ratios (content ratios) corresponding to those described in the above-mentioned "Mode for carrying out the invention". ), Physical property values, parameters, etc. can be replaced with the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess"). can. In addition, unless otherwise specified in the following description, "part" and "%" are based on mass.

1. 1. Production of metal layer Example 1
An ultraviolet curable resin made of an acrylic resin was applied to one surface in the thickness direction of a base material made of a PET film roll (manufactured by Toray Industries, Inc., thickness 50 μm) and cured by ultraviolet irradiation. As a result, a hard coat layer having a thickness of 2 μm was formed, and a base material was prepared.

This base material was placed in a vacuum sputtering apparatus and sufficiently evacuated so that the ultimate vacuum degree was 0.9 × 10 ^-4 Pa, and the base material was degassed. Then, while transporting the base material along the film forming roll, in a low pressure environment in which krypton atoms (sputtering gas) are present, a sputtering method targeting copper (Cu) is performed on one side of the base material in the thickness direction. , A metal layer having a thickness of 70 nm was formed (arranged). As a result, a metal layer was manufactured. The sputtering conditions are as follows.
<Sputtering conditions>
Power supply: DC power supply Target horizontal magnetic field strength: 90mT
Film formation pressure: 0.4 Pa
Film formation roll temperature: -8 ° C

Example 2
A metal layer was produced in the same manner as in Example 1 except that the thickness of the metal layer was changed to 87 nm.

Example 3
A metal layer was produced in the same manner as in Example 1 except that the target was changed to aluminum (Al) and the horizontal magnetic field strength of the target was changed to 50 mT.

Comparative Example 1
A metal layer was produced in the same manner as in Example 1 except that the sputtering gas was changed to argon gas.

Comparative Example 2
A metal layer was produced in the same manner as in Example 2 except that the sputtering gas was changed to argon gas.

Comparative Example 3
A metal layer was produced in the same manner as in Example 3 except that the sputtering gas was changed to argon gas.

2. 2. Evaluation <Thickness of metal layer>
For each of the metal layers of each example and each comparative example, a cross-sectional sample for TEM was prepared by a FIB microsampling method using a FIB device (manufactured by Hitachi, "FB2200", acceleration voltage: 10 kV). Next, the thickness of the metal layer was measured by observing the cross section using a field emission transmission electron microscope (FE-TEM, manufactured by JOEL, "JEM-2800", acceleration voltage: 200 kV). The results are shown in Table 1.

<Measurement of surface resistance value>
The surface resistance value (hereinafter referred to as surface resistance value A) of each of the metal layers of each example and each comparative example was measured by a four-terminal method in accordance with JIS K7194. The results are shown in Table 1.

Next, the metal layers of each Example and each Comparative Example were heated at 80 ° C. for 3 hours, and the surface resistance value (hereinafter referred to as surface resistance value B) was measured by the same method. The results are shown in Table 1.

Separately, the metal layers of each Example and each Comparative Example were heated at 140 ° C. for 1 hour, and the surface resistance value (hereinafter referred to as surface resistance value C) was measured by the same method. The results are shown in Table 1.
<Heating stability>
The heating stability was evaluated for the metal layers of each Example and each Comparative Example.

Specifically, the ratio of resistance change (B / A) and the ratio of resistance change (C / A) were calculated based on the following formulas (2) and (3).

Ratio of resistance change (B / A) = surface resistance value B / surface resistance value A (2)
Ratio of resistance change (C / A) = surface resistance value C / surface resistance value A (3)
The resistance change ratio (B / A) and the resistance change ratio (C / A) indicate the change in the surface resistance value after heating with respect to the surface resistance value before heating, and the resistance change ratio (B / A). And if the ratio of resistance change (C / A) is small, it means that the increase in the resistance value of the metal layer can be suppressed before and after heating (excellent in heating stability).

<Measurement of resistivity>
The specific resistance of each of the metal layers of each example and each comparative example was calculated based on the following formula (4).

Specific resistance of metal layer = thickness of metal layer x surface resistance value of metal layer A (4)
<Identification of krypton atom and argon atom>
The presence or absence of krypton and argon atoms contained in the metal layers of each example and each comparative example was analyzed by Rutherford Backscattering Spectroscopy (RBS). The presence or absence of a krypton atom or an argon atom in the metal layer was determined by determining the element ratio for the three elements of the detection element, the metal element (Cu or Al), Ar, and Kr. As a result of the evaluation, it was confirmed that the metal layers of Examples 1 to 3 contained krypton atoms, and the metal layers of Comparative Examples 1 to 3 contained argon atoms.
<Device used>
Pelletron 3SDH (manufactured by National Electricals Corporation)
<Measurement conditions>
Incident ion: 4He ⁺⁺
Incident energy: 2300 keV
Incident angle: 0 deg
Scattering angle: 160deg
Sample current: 5nA
Beam diameter: 2 mmφ
In-plane rotation: No irradiation amount: 75 μC

3. 3. Discussion In Example 1 and Comparative Example 1, the metal layer is manufactured by the same procedure except that the sputtering gas is different.

Example 1 in which krypton is used as the sputtering gas has a smaller resistance change ratio (B / A) and resistance change ratio (C / A) than Comparative Example 1 in which argon is used.

From this, it can be seen that if krypton is used as the sputtering gas, the heating stability is excellent.

This also applies to the comparison between Example 2 and Comparative Example 2 and the comparison between Example 3 and Comparative Example 3.

1 Metal layer

Claims (11)

As a main component, it contains a metal belonging to the 3rd period and / or the 4th period, and
A metal layer comprising a krypton atom and / or a xenon atom. The metal layer according to claim 1, wherein the metal layer has conductivity. The metal layer according to claim 1 or 2, characterized in that it has a pattern shape. A touch sensor comprising the metal layer according to any one of claims 1 to 3. A dimming element comprising the metal layer according to any one of claims 1 to 3. A photoelectric conversion element comprising the metal layer according to any one of claims 1 to 3. A heat ray control member comprising the metal layer according to any one of claims 1 to 3. An antenna comprising the metal layer according to any one of claims 1 to 3. An electromagnetic wave shielding member comprising the metal layer according to any one of claims 1 to 3. An image display device comprising the metal layer according to any one of claims 1 to 3. A method for producing a metal layer, which comprises forming a metal layer by a sputtering method targeting a metal belonging to the 3rd period and / or the 4th period in the presence of krypton and / or xenon.

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