KR20230086668A - Metal layer, touch sensor, light control element, photoelectric conversion element, heat wire control member, antenna, electromagnetic shield member, image display device, and manufacturing method of metal layer - Google Patents

Abstract

The metal layer contains, as a main component, a metal belonging to the third period and/or the fourth period, and further includes a krypton atom and/or a xenon atom.

Description

Metal layer, touch sensor, light control element, photoelectric conversion element, heat wire control member, antenna, electromagnetic shield member, image display device, and manufacturing method of metal layer

The present invention relates to a metal layer, a touch sensor, a light control element, a photoelectric conversion element, a heat ray control member, an antenna, an electromagnetic wave shield member, an image display device, and a method for manufacturing the metal layer, and more particularly, to a metal layer and a touch comprising the metal layer. A sensor, a light control element including the metal layer, a photoelectric conversion element including the metal layer, a heat wire control member including the metal layer, an antenna including the metal layer, an electromagnetic shield member including the metal layer, and an image including the metal layer It relates to a display device and a method of manufacturing a metal layer.

In recent years, it is known that a metal layer is used as an electrode member such as a touch panel.

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

Japanese Unexamined Patent Publication No. 2012-234796

On the other hand, when processing a metal layer 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 before and after heating (excellent heating stability).

The present invention provides a metal layer with excellent heating stability, a touch sensor including the metal layer, a light control element including the metal layer, a photoelectric conversion element including the metal layer, a heat ray control member including the metal layer, and an antenna including the metal layer. , It is to provide an electromagnetic shielding member provided with the metal layer, an image display device provided with the metal layer, and a manufacturing method for the metal layer excellent in heat stability.

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

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

This invention [3] contains the metal layer of [1] or [2] which has a pattern shape.

This invention [4] includes the touch sensor provided with the metal layer as described in any one of said [1]-[3].

This invention [5] includes the light control element provided with the metal layer as described in any one of said [1]-[3].

This invention [6] includes the photoelectric conversion element provided with the metal layer as described in any one of said [1]-[3].

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

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

This invention [9] includes the electromagnetic shielding member provided with the metal layer as described in any one of said [1]-[3].

This invention [10] includes the image display apparatus provided with the metal layer as described in any one of said [1]-[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 third period and/or the fourth period in the presence of krypton and/or xenon.

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

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

In this method, since krypton and/or xenon having an atomic weight larger than that of argon is used instead of argon as the sputtering gas, introduction of atoms (krypton atoms and/or xenon atoms) derived from the sputtering gas into the metal layer can be suppressed. there is.

In this way, a metal layer having excellent heating stability can be manufactured.

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

In addition, since the metal layer, touch sensor, light control element, photoelectric conversion element, heat ray control member, antenna, electromagnetic shield member, and image display device of the present invention are provided with the metal layer of the present invention, heat stability is excellent.

1 is a schematic diagram showing one embodiment of a metal layer of the present invention.
2A and 2B are schematic diagrams showing one embodiment of a method for producing a metal layer of the present invention, FIG. 2A shows a step of preparing a substrate, and FIG. 2B shows a process in the presence of a sputtering gas (krypton and/or xenon). In this case, a metal layer is formed (arranged) on one side of the substrate in the thickness direction by a sputtering method targeting a metal belonging to the third cycle and/or the fourth cycle.
Fig. 3 is a schematic view showing an embodiment 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 sheet shape) having a predetermined thickness, extending 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 atoms derived from a trace amount of sputtering gas, and is preferably composed of a metal and atoms derived from sputtering gas. Specifically, the metal layer 1 contains a metal as a main component and an atom derived from a sputtering gas as a minor 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 third cycle and/or the fourth cycle. In short, the metal layer 1 contains, as a main component, a metal belonging to the third cycle and/or the fourth cycle.

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

Metals belonging to the fourth cycle include, for example, titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc ( Zn), gallium (Ga), and the like, preferably copper (Cu).

The metal belonging to the 3rd cycle and/or the 4th cycle can be used individually or in combination of 2 or more types.

The metal may contain other metals as subcomponents.

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

Examples of metals belonging to the fifth period include zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), indium ( In) and the like.

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

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

The metal preferably does not contain other metals and is composed of a metal belonging to the third cycle and/or the fourth cycle, more preferably composed of a metal belonging to the third cycle or a metal belonging to the fourth cycle. made up of

The atoms derived from the sputtering gas are atoms introduced into the metal layer 1 when the metal layer 1 is formed by the sputtering method, as described later in detail, and are atoms derived from the sputtering gas. Specifically, , krypton atoms and/or xenon atoms. In short, the metal layer 1 contains krypton atoms and/or xenon atoms.

As the atom derived from the sputtering gas, preferably a krypton atom or a xenon atom, more preferably a krypton atom.

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 fluorescence X-ray analysis or Rutherford Backscattering Spectrometry (abbreviated abbreviation RBS) described later in the Examples.

The lower limit of the content is a ratio corresponding to when the presence of krypton atoms and/or xenon atoms can be confirmed by X-ray fluorescence spectrometry or Rutherford backscattering analysis, and is at least 0.00001 atomic% 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, and further It is preferably 300 nm or less, particularly preferably 100 nm or less.

The measuring method of the thickness of the metal layer 1 is explained in detail in the Example mentioned later.

Next, the manufacturing method of the metal layer 1 is demonstrated with reference to FIG. 2A and FIG. 2B.

In this manufacturing method, in the presence of a sputtering gas (krypton and/or xenon), the metal layer is subjected to a sputtering method targeting the above-mentioned metal (a metal containing a metal belonging to the third cycle and/or fourth cycle as a main component). (1) form

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

The base material 2 has a film shape.

As base material 2, a polymer film is mentioned, for example from a flexible viewpoint. Examples of the material of the polymer film include olefin resins such as polyethylene, polypropylene, and cycloolefin polymers; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; For example, (meth)acrylic resins (acrylic resins and/or methacrylic resins) such as polymethacrylates, such as polycarbonate resins, polyethersulfone resins, polyarylate resins, melamine resins, and polyamide resins. , polyimide resins, cellulose resins, polystyrene resins and the like, preferably polyester resins, more preferably polyethylene terephthalate (PET).

The thickness of the substrate 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 It is preferably 100 μm or less, more preferably 60 μm or less.

The thickness of the substrate 2 can be measured using a dial gauge (“DG-205” manufactured by PEACOCK).

Further, the substrate 2 may be subjected to surface treatment such as hard coat treatment, if necessary, from the viewpoint of imparting scratch resistance.

Subsequently, as shown in FIG. 2B, in the presence of a sputtering gas (krypton and/or xenon), a metal layer 1 is formed on one surface of the substrate 2 in the thickness direction by a sputtering method using the metal as a target. (placement)

Specifically, in the sputtering apparatus, while conveying the base material 2 along the circumferential surface of a film-forming roll, while making one side of the thickness direction of the base material 2 face a target made of the above metal, a sputtering gas (preferably Sputtering is performed in the presence of krypton or xenon, more preferably krypton.

Examples of sputtering include a two-pole sputtering method, an ECR (electron cyclotron resonance) sputtering method, a magnetron sputtering method, and an ion beam sputtering method.

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

The partial pressure of krypton and/or xenon in the sputtering device 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 is 5 Pa or less, more preferably 1 Pa or less.

The pressure (film formation pressure) in the sputtering device 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. For example, it is 15 Pa or less, preferably 10 Pa or less, more preferably 5 Pa or less, even more preferably 1 Pa or less, and particularly preferably 0.5 Pa or less.

In addition, as a power supply used for sputtering, a direct current (DC) power supply, an alternating current medium frequency (AC/MF) power supply, a high frequency (RF) power supply, and a high frequency power supply superimposed on a direct current power supply are exemplified, preferably. direct current (DC) power sources.

The intensity 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. The atomic content of the sputtering gas in the metal layer 1 can be adjusted by adjusting the intensity of the horizontal magnetic field on the target surface to the above range.

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, and furthermore It is preferably 40°C or less, particularly preferably less than 10°C.

By the above sputtering, the metal layer 1 is formed (arranged) on one side of the substrate 2 in the thickness direction. Thereby, while the metal layer 1 is obtained, the laminated body 3 which equips the base material 2 and the metal layer 1 sequentially toward one side of the thickness direction is obtained.

And such a metal layer 1 has conductivity.

If the metal layer 1 has conductivity, it can be suitably used as an electrode member included in a touch sensor, light control element, photoelectric conversion element, heat wire control member, antenna, electromagnetic shield member, image display device, etc. described later.

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

In addition, 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, more preferably 2.00 Ω/□. or less, more preferably 1.70 Ω/□ or less, and usually more than 0.001 Ω/□, and also 0.1 Ω/□ or more, preferably 1.00 Ω/□ or more.

In addition, surface resistance value can be measured by the 4-probe method based on JISK7194.

In addition, when the metal is made of copper (Cu), the specific resistance of the metal layer 1 is, for example, 10 × 10 ^-6 Ω cm or less, preferably 2.50 × 10 ^-6 Ω cm or less, more preferably It is preferably 2.40 × 10 ^-6 Ω·cm or less, more preferably 2.30 × 10 ^-6 Ω·cm or less, particularly preferably 2.05 × 10 ^-6 Ω·cm or less, and, for example, 0.10 × 10 ^-6 Ω·cm or more.

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

In addition, specific resistance is computable based on following formula (1) using the surface resistance value and the thickness of the metal layer 1 calculated|required by the 4-terminal method based on JISK7194.

Resistivity of the metal layer (1) = thickness of the metal layer (1) × surface resistance value of the metal layer (1) (1)

In addition, when the metal layer 1 is produced by the above sputtering method, atoms derived from the sputtering gas are introduced into the metal layer 1.

However, in this method, since krypton and/or xenon having an atomic weight larger than that of argon is used instead of the normally used argon as the sputtering gas, introduction of atoms derived from the sputtering gas into the metal layer 1 can be suppressed. there is.

In short, such a metal layer 1 contains krypton atoms and/or xenon atoms, but as described above, since the amount of krypton atoms and/or xenon atoms introduced is suppressed, this metal layer 1 is heated Before and after, the increase in resistance value can be suppressed (in other words, this metal layer 1 is excellent in heating stability).

Moreover, such a metal layer 1 is excellent in heat stability as mentioned above, while containing the metal belonging to the 3rd period and/or the 4th period as a main component. In short, according to this method, the metal layer 1 excellent in heating stability can be manufactured without using expensive metals such as gold (Au) (a metal belonging to the 6th cycle) as a main component, for example. 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 substrate 2 . The resin layer is, for example, an adhesive layer or an adhesive layer for bonding the metal layer 1 and other members together, and is, for example, a coating layer that protects the metal layer 1. The material of the resin layer is not limited, and known resins such as acrylic resins can be used. In addition, the resin layer may contain a UV absorber or a corrosion inhibitor. Although there is no limitation on the material of the ultraviolet absorber or corrosion inhibitor, examples thereof include benzotriazole-based compounds disclosed in Japanese Unexamined Patent Publication No. 2015-022397.

Moreover, as shown in FIG. 3, in the laminated body 3, the metal layer 1 can also be patterned. In short, the metal layer 1 has a pattern shape.

To pattern the metal layer 1, the metal layer 1 is etched, for example. Thereby, the laminated body 3 has the pattern part 4 which has the metal layer 1, and the non-pattern part 5 which does not have the metal layer 1. The laminated body 3 may be equipped with a resin layer (not shown) on the upper surface of the pattern part 4 and the non-pattern part 5. The resin layer is, for example, an adhesive layer or an adhesive layer for bonding the layered product 3 and other members together, and is, for example, a coating layer that protects the pattern portion 4 of the layered product 3. Moreover, a ultraviolet absorber, a corrosion inhibitor, and a migration inhibitor may be contained in a resin layer, For example, the benzotriazole type compound etc. which are disclosed in Unexamined-Japanese-Patent No. 2015-022397 can be contained.

And, this metal layer 1 is used for various purposes, for example, a touch sensor, a light control element (voltage driven light control element such as PDLC, PNLC or SPD, or current drive type such as electrochromic (EC) light control element), photoelectric conversion element (solar cell element represented by organic thin-film solar cell or dye-sensitized solar cell), heat control member (near-infrared reflecting and/or absorbing member or far-infrared reflecting and/or absorbing member), antenna (light Transmissive antenna), an electromagnetic shield member, a heater member, an electrode member provided in an image display device, and the like.

Since such a touch sensor, a light control element, a photoelectric conversion element, a heat wire control member, an antenna, an electromagnetic shield member, a heater member, and an image display device are provided with the metal layer 1 of the present invention, they are excellent in heating stability.

Example

Specific numerical values such as the blending ratio (content ratio), physical property value, and parameter used in the following description are the blending ratio (content ratio) corresponding to those described in the above "mode for carrying out the invention", It can be replaced with the upper limit value (numerical value defined as "below" or "less than") or lower limit value (numerical value defined as "above" or "exceed") of the corresponding description, such as physical property value or parameter. In addition, in the description below, "parts" and "%" are based on mass unless otherwise specified.

1. Preparation of the metal layer

Example 1

An ultraviolet curable resin made of an acrylic resin was applied to one side in the thickness direction of a substrate made of a PET film roll (manufactured by Toray Industries, 50 μm in thickness) and cured by ultraviolet irradiation. In this way, a hard coat layer having a thickness of 2 μm was formed, and a base material was prepared.

This substrate was placed in a vacuum sputtering apparatus, and the substrate was subjected to degassing by sufficiently evacuating the substrate so that the vacuum degree reached was 0.9 × 10 ^-4 Pa. Thereafter, while transporting the substrate along the film forming roll, in a low-pressure environment in which krypton atoms (sputtering gas) exist, a sputtering method targeting copper (Cu) is applied to one side of the thickness direction of the substrate to form a thickness of 70%. A metal layer of nm was formed (placed). Thus, a metal layer was prepared. In addition, the conditions of sputtering are as follows.

<Conditions of sputtering>

Power: DC power

Horizontal magnetic field strength of target: 90 mT

Film formation air pressure: 0.4 Pa

Filming roll temperature: -8 ℃

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 manufactured 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. Evaluation

<thickness of metal layer>

For the metal layers of each Example and each Comparative Example, cross-sectional samples for TEM were prepared by the FIB microsampling method using an FIB device ("FB2200" manufactured by Hitachi, acceleration voltage: 10 kV). Subsequently, cross-section observation was performed using a field emission type transmission electron microscope (FE-TEM, manufactured by JOEL, "JEM-2800", acceleration voltage: 200 kV), and the thickness of the metal layer was measured. The results are shown in Table 1.

<Measurement of surface resistance value>

About the metal layer of each Example and each comparative example, the surface resistance value (it is hereafter called surface resistance value A) was measured by the 4-terminal method based on JISK7194. The results are shown in Table 1.

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

Separately, the metal layer of each example and each comparative example was heated at 140°C for 1 hour, and the surface resistance value (hereinafter referred to as surface resistance value C) was measured in the same manner. The results are shown in Table 1.

<heating stability>

Heating stability was evaluated for the metal layer of each Example and each Comparative Example.

Specifically, the resistance change ratio (B/A) and the resistance change ratio (C/A) were calculated based on the following formula (2) and the following formula (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 ratio of resistance change (B/A) and the ratio of resistance change (C/A) represent the change in surface resistance value after heating with respect to the surface resistance value before heating, and the ratio of resistance change (B/A) and resistance When the change ratio (C/A) is small, it means that the increase in the resistance value of the metal layer can be suppressed before and after heating (heating stability is excellent).

<Measurement of resistivity>

With respect to the metal layer of each Example and each Comparative Example, the specific resistance was calculated based on the following formula (4).

Resistivity of the metal layer = thickness of the metal layer × surface resistance of the metal layer A (4)

<Identification of krypton atom and argon atom>

The presence or absence of krypton atoms and argon atoms contained in the metal layers of each example and each comparative example was analyzed by Rutherford backscattering spectroscopy (RBS). The existence or nonexistence of krypton atoms or argon atoms in the metal layer was determined by determining the element ratios of three elements, metal elements (Cu or Al), Ar, and Kr, which are detection elements. As a result of the evaluation, it was confirmed that krypton atoms were contained in the metal layers of Examples 1 to 3, and argon atoms were contained in the metal layers of Comparative Examples 1 to 3.

＜Using device＞

Pelletron 3SDH (manufactured by National Electrostatics Corporation)

<measurement conditions>

Incident ion: 4He ⁺⁺

Incident energy: 2300 keV

Angle of incidence: 0 deg

Scattering angle: 160 deg

Sample current: 5 nA

Beam diameter: 2 mmφ

In-plane rotation: none

Irradiation: 75μC

3. Consideration

In Example 1 and Comparative Example 1, the metal layer was manufactured in the same procedure except that the sputtering gas was different.

Example 1 using krypton as the sputtering gas has smaller resistance change ratios (B/A) and resistance change ratios (C/A) than Comparative Example 1 using argon.

From this, it can be seen that the use of krypton as the sputtering gas provides excellent heating stability.

In addition, this is the same also in the comparison of Example 2 and Comparative Example 2, and the comparison of Example 3 and Comparative Example 3.

In addition, although the said invention was provided as embodiment of an illustration of this invention, this is only a mere illustration and it must not interpret it limitedly. Modifications of the present invention, which are clear to those skilled in the art in the art, are included in the scope of the later claims.

Metal layers, touch sensors, light control elements, photoelectric conversion elements, heat wire control members, antennas, electromagnetic shield members, image display devices, and metal layer manufacturing methods are preferably used as electrode members such as touch panels, for example.

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, characterized in that it comprises krypton atoms and/or xenon atoms. According to claim 1,
A metal layer characterized by having conductivity. According to claim 1,
A metal layer characterized by having a pattern shape. A touch sensor comprising the metal layer according to claim 1 . A light control element comprising the metal layer according to claim 1 . A photoelectric conversion element comprising the metal layer according to claim 1. A heat wire control member comprising the metal layer according to claim 1 . An antenna comprising the metal layer according to claim 1. An electromagnetic shielding member characterized by comprising the metal layer according to claim 1. An image display device comprising the metal layer according to claim 1 . A method for producing a metal layer characterized by forming a metal layer by a sputtering method using a metal belonging to the third period and/or the fourth period as a target in the presence of krypton and/or xenon.

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