WO2022080011A1 - 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

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 Download PDF

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WO2022080011A1
WO2022080011A1 PCT/JP2021/030938 JP2021030938W WO2022080011A1 WO 2022080011 A1 WO2022080011 A1 WO 2022080011A1 JP 2021030938 W JP2021030938 W JP 2021030938W WO 2022080011 A1 WO2022080011 A1 WO 2022080011A1
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Prior art keywords
metal layer
metal
less
krypton
period
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PCT/JP2021/030938
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French (fr)
Japanese (ja)
Inventor
望 藤野
泰介 鴉田
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日東電工株式会社
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Priority to CN202180069697.6A priority Critical patent/CN116326230A/en
Priority to KR1020237010194A priority patent/KR20230086668A/en
Publication of WO2022080011A1 publication Critical patent/WO2022080011A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields

Definitions

  • 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.
  • the present invention relates to an image display device provided and a method for manufacturing a metal layer.
  • 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).
  • the metal layer when processing the 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 (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.
  • the method for producing a metal layer of the present invention forms 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.
  • atoms derived from the sputtering gas are incorporated into the metal layer.
  • 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.
  • the metal layer of the present invention is excellent in heating stability.
  • the metal layer, touch sensor, dimming element, photoelectric conversion element, heat ray control member, antenna, electromagnetic wave shielding member, and 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.
  • 2A and 2B are schematic views showing an embodiment of the method for producing a metal layer of the present invention,
  • FIG. 2A shows a step of preparing a substrate, and
  • FIG. 2B shows a sputtering gas (krypton and / or).
  • 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 3rd cycle and / or the 4th cycle in the presence of xenon) 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.
  • 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 is preferably composed of a metal and an atom derived from the sputtering gas.
  • 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 a metal belonging to the 3rd period and / or the 4th period as a main component. 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 can also contain other metals as an accessory component.
  • 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.
  • 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.
  • Examples of the atom derived from the sputtering gas include a krypton atom or a xenon atom, and 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 by, for example, 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.
  • the metal 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).
  • a sputtering gas krypton and / or xenon
  • the base material 2 is prepared.
  • 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, and polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate and polyethylene naphthalate, and (meth) such as polymethacrylate.
  • Acrylic resin (acrylic resin and / or methacrylic resin), for example, polycarbonate resin, polyether sulfone 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 ⁇ m or more, preferably 10 ⁇ m or more, preferably 30 ⁇ m or more, and for example, 300 ⁇ m or less, preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably. It is 60 ⁇ m or less.
  • the thickness of the base material 2 can be measured using a dial gauge ("DG-205" manufactured by PEACOCK).
  • the base material 2 can be subjected to a surface treatment such as a hard coat treatment from the viewpoint of imparting scratch resistance, if necessary.
  • 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.
  • a sputtering gas krypton and / or xenon
  • 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.
  • a reactive gas such as oxygen can be present in addition to krypton and / or xenon.
  • 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.
  • DC direct current
  • AC / MF alternating current medium frequency
  • RF high frequency
  • DC direct current
  • 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.
  • 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.
  • the metal layer 1 is formed (arranged) on one side 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.
  • Such a metal layer 1 has conductivity.
  • the metal layer 1 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.
  • the surface resistance value of the metal layer 1 is, for example, 5 ⁇ / ⁇ or less, preferably 0.5 ⁇ / ⁇ or less, more preferably 0.35 ⁇ / ⁇ when the metal is made of copper (Cu). Below, it is more preferably 0.30 ⁇ / ⁇ or less, more preferably 0.23 ⁇ / ⁇ or less, and usually 0.001 ⁇ / ⁇ or more, and 0.01 ⁇ / ⁇ or more, preferably 0.01 ⁇ / ⁇ or more. It is 0.1 ⁇ / ⁇ or more.
  • the surface resistance value of the metal layer 1 is, for example, 10 ⁇ / ⁇ or less, preferably 5.00 ⁇ / ⁇ or less, and more preferably 2.00 ⁇ / ⁇ or less. It is more preferably 1.70 ⁇ / ⁇ or less, and usually exceeds 0.001 ⁇ / ⁇ , and is 0.1 ⁇ / ⁇ or more, preferably 1.00 ⁇ / ⁇ or more.
  • the surface resistance value can be measured by the 4-terminal method in accordance with JIS K7194.
  • the resistivity of the metal layer 1 is, for example, 10 ⁇ 10 -6 ⁇ ⁇ cm or less, preferably 2.50 ⁇ 10 -6 ⁇ ⁇ cm or less. It is preferably 2.40 ⁇ 10 -6 ⁇ ⁇ cm or less, more preferably 2.30 ⁇ 10 -6 ⁇ ⁇ cm or less, and particularly preferably 2.05 ⁇ 10 -6 ⁇ ⁇ cm or less, and also. For example, 0.10 ⁇ 10 -6 ⁇ ⁇ cm or more.
  • the resistivity of the metal layer 1 is, for example, 20 ⁇ 10 -6 ⁇ ⁇ cm or less, preferably 9.0 ⁇ 10 -6 ⁇ ⁇ cm or less. It is preferably 7.0 ⁇ 10 -6 ⁇ ⁇ cm or less, and is, for example, 0.10 ⁇ 10 -6 ⁇ ⁇ cm or more, preferably 1.0 ⁇ 10 -6 ⁇ ⁇ 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.
  • 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).
  • 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.
  • Au gold
  • 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.
  • 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.
  • the metal layer 1 can be patterned in the laminated body 3. That is, the metal layer 1 has a pattern shape.
  • 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.
  • 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 Japanese Patent Application Laid-Open No. 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, or the like.
  • 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
  • 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
  • a dimming element a photoelectric conversion element
  • a heat ray control member an antenna
  • an electromagnetic wave shielding member a heater member
  • an image display device include the metal layer 1 of the present invention, they are excellent in heating stability.
  • 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 ⁇ m) and cured by ultraviolet irradiation. As a result, a hard coat layer having a thickness of 2 ⁇ m 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.
  • 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.
  • 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).
  • 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 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.
  • the metal layers of Examples 1 to 3 contained krypton atoms
  • 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.
  • the method for manufacturing 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 metal layer is suitably used as an electrode member such as a touch panel, for example.

Abstract

This metal layer 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.

Description

金属層、タッチセンサ、調光素子、光電変換素子、熱線制御部材、アンテナ、電磁波シールド部材、画像表示装置および金属層の製造方法Manufacturing method of metal layer, touch sensor, dimming element, photoelectric conversion element, heat ray control member, antenna, electromagnetic wave shielding member, image display device and metal layer
　本発明は、金属層、タッチセンサ、調光素子、光電変換素子、熱線制御部材、アンテナ、電磁波シールド部材、画像表示装置および金属層の製造方法に関し、詳しくは、金属層、その金属層を備えるタッチセンサ、その金属層を備える調光素子、その金属層を備える光電変換素子、その金属層を備える熱線制御部材、その金属層を備えるアンテナ、その金属層を備える電磁波シールド部材、その金属層を備える画像表示装置、および、金属層の製造方法に関する。 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.
　近年、タッチパネルなどの電極部材として、金属層が用いられることが知られている。 In recent years, it is known that a metal layer is used as an electrode member for a touch panel or the like.
　このような金属層として、例えば、アルゴンガス存在下で、スパッタリングにより成膜された導電性金属層が提案されている（例えば、特許文献１参照。）。 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).
特開２０１２－２３４７９６号公報Japanese Unexamined Patent Publication No. 2012-234996
　一方、金属層を電極部材に加工する際に、金属層を加熱する場合がある。このような場合には、加熱前後において、金属層の抵抗値の増加を抑制すること（加熱安定性に優れること）が要求される。 On the other hand, when processing the 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 (excellent in heating stability) before and after heating.
　本発明は、加熱安定性に優れる金属層、その金属層を備えるタッチセンサ、その金属層を備える調光素子、その金属層を備える光電変換素子、その金属層を備える熱線制御部材、その金属層を備えるアンテナ、その金属層を備える電磁波シールド部材、その金属層を備える画像表示装置、および、加熱安定性に優れる金属層の製造方法を提供することにある。 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.
　本発明［１］は、主成分として、第３周期および／または第４周期に属する金属を含み、かつ、クリプトン原子および／またはキセノン原子を含む、金属層である。 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.
　本発明［２］は、導電性を有する、上記［１］に記載の金属層を含んでいる。 The present invention [2] includes the metal layer according to the above [1], which has conductivity.
　本発明［３］は、パターン形状を有する、上記［１］または［２］に記載の金属層を含んでいる。 The present invention [3] includes the metal layer according to the above [1] or [2], which has a pattern shape.
　本発明［４］は、上記［１］～［３］のいずれか一項に記載の金属層を備える、タッチセンサを含んでいる。 The present invention [4] includes a touch sensor including the metal layer according to any one of the above [1] to [3].
　本発明［５］は、上記［１］～［３］のいずれか一項に記載の金属層を備える、調光素子を含んでいる。 The present invention [5] includes a dimming element including the metal layer according to any one of the above [1] to [3].
　本発明［６］は、上記［１］～［３］のいずれか一項に記載の金属層を備える、光電変換素子を含んでいる。 The present invention [6] includes a photoelectric conversion element including the metal layer according to any one of the above [1] to [3].
　本発明［７］は、上記［１］～［３］のいずれか一項に記載の金属層を備える、熱線制御部材を含んでいる。 The present invention [7] includes a heat ray control member including the metal layer according to any one of the above [1] to [3].
　本発明［８］は、上記［１］～［３］のいずれか一項に記載の金属層を備える、アンテナを含んでいる。 The present invention [8] includes an antenna including the metal layer according to any one of the above [1] to [3].
　本発明［９］は、上記［１］～［３］のいずれか一項に記載の金属層を備える、電磁波シールド部材を含んでいる。 The present invention [9] includes an electromagnetic wave shielding member including the metal layer according to any one of the above [1] to [3].
　本発明［１０］は、上記［１］～［３］のいずれか一項に記載の金属層を備える、画像表示装置を含んでいる。 The present invention [10] includes an image display device including the metal layer according to any one of the above [1] to [3].
　本発明［１１］は、クリプトンおよび／またはキセノン存在下において、第３周期および／または第４周期に属する金属をターゲットとするスパッタリング法によって、金属層を形成する、金属層の製造方法である。 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.
　本発明の金属層の製造方法は、クリプトンおよび／またはキセノン存在下において、第３周期および／または第４周期に属する金属をターゲットとするスパッタリング法によって、金属層を形成する。 The method for producing a metal layer of the present invention forms 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.
　スパッタリング法によって、金属層を形成する場合には、スパッタリングガスに由来する原子が金属層に取り込まれる。 When a metal layer is formed by the sputtering method, atoms derived from the sputtering gas are incorporated into the metal layer.
　この方法では、スパッタリングガスとして、アルゴンに代えて、アルゴンよりも原子量の大きいクリプトンおよび／またはキセノンを用いるため、スパッタリングガスに由来する原子（クリプトン原子および／またはキセノン原子）が金属層に取り込まれることを抑制できる。 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.
　これにより、加熱安定性に優れる金属層を製造できる。 This makes it possible to manufacture a metal layer with excellent heating stability.
　そのため、本発明の金属層は、加熱安定性に優れる。 Therefore, the metal layer of the present invention is excellent in heating stability.
　また、本発明の金属層、タッチセンサ、調光素子、光電変換素子、熱線制御部材、アンテナ、電磁波シールド部材、画像表示装置は、本発明の金属層を備えるため、加熱安定性に優れる。 Further, since the metal layer, touch sensor, dimming element, photoelectric conversion element, heat ray control member, antenna, electromagnetic wave shielding member, and image display device of the present invention include the metal layer of the present invention, they are excellent in heating stability.
図１は、本発明の金属層の一実施形態を示す概略図である。FIG. 1 is a schematic view showing an embodiment of the metal layer of the present invention. 図２Ａおよび図２Ｂは、本発明の金属層の製造方法の一実施形態を示す概略図であり、図２Ａは、基材を準備する工程を示し、図２Ｂは、スパッタリングガス（クリプトンおよび／またはキセノン）存在下において、第３周期および／または第４周期に属する金属をターゲットとするスパッタリング法によって、基材の厚み方向一方面に、金属層を形成（配置）する工程を示す。2A and 2B are schematic views showing an embodiment of the method for producing a metal layer of the present invention, FIG. 2A shows a step of preparing a substrate, and FIG. 2B shows a sputtering gas (krypton and / or). 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 3rd cycle and / or the 4th cycle in the presence of xenon) is shown. 図３は、図２Ｂに示す積層体の金属層をパターン化した態様を示す概略図である。FIG. 3 is a schematic view showing an aspect in which the metal layer of the laminate shown in FIG. 2B is patterned.
　金属層１は、図１に示すように、所定の厚みを有するフィルム形状（シート形状を含む）を有し、厚み方向と直交する面方向に延び、平坦な上面および平坦な下面を有する。 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.
　金属層１は、金属と、微量のスパッタリングガスに由来する原子とを含み、好ましくは、金属と、スパッタリングガスに由来する原子とからなる。具体的には、金属層１は、主成分としての金属と、微量成分としてのスパッタリングガスに由来する原子とを含み、好ましくは、金属とスパッタリングガスに由来する原子とからなる。より具体的には、金属層１では、金属マトリックス中に、微量のスパッタリングガスに由来する原子が存在する。 The metal layer 1 contains a metal and an atom derived from a trace amount of sputtering gas, and is preferably composed of 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.
　金属は、主成分として、第３周期および／または第４周期に属する金属を含む。つまり、金属層１は、主成分として、第３周期および／または第４周期に属する金属を含む。 The metal contains a metal belonging to the 3rd period and / or the 4th period as a main component. That is, the metal layer 1 contains a metal belonging to the third period and / or the fourth period as a main component.
　第３周期に属する金属としては、例えば、マグネシウム（Ｍｇ）、アルミニウム（Ａｌ）、ケイ素（Ｓｉ）、リン（Ｐ）などが挙げられ、好ましくは、アルミニウム（Ａｌ）が挙げられる。 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.
　第４周期に属する金属としては、例えば、チタン（Ｔｉ）、クロム（Ｃｒ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、ガリウム（Ｇａ）などが挙げられ、好ましくは、銅（Ｃｕ）が挙げられる。 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.
　第３周期および／または第４周期に属する金属は、単独使用または２種以上併用することができる。 Metals belonging to the 3rd cycle and / or the 4th cycle can be used alone or in combination of two or more.
　金属は、副成分として、他の金属を含むこともできる。 The metal can also contain other metals as an accessory component.
　他の金属としては、例えば、第５周期に属する金属、第６周期に属する金属などが挙げられる。 Examples of other metals include metals belonging to the 5th period and metals belonging to the 6th period.
　第５周期に属する金属としては、例えば、ジルコニウム（Ｚｒ）、ニオブ（Ｎｂ）、モリブデン（Ｍｏ）、ルテニウム（Ｒｕ）、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）、銀（Ａｇ）、インジウム（Ｉｎ）などが挙げられる。 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.
　第６周期に属する金属としては、例えば、タンタル（Ｔａ）、タングステン（Ｗ）、レニウム（Ｒｅ）、オスミウム（Ｏｓ）、イリジウム（Ｉｒ）、白金（Ｐｔ）、金（Ａｕ）などが挙げられる。 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.
　他の金属は、単独使用または２種以上併用することができる。 Other metals can be used alone or in combination of two or more.
　金属は、好ましくは、他の金属を含まず、第３周期および／または第４周期に属する金属からなり、より好ましくは、第３周期に属する金属からなるか、または、第４周期に属する金属からなる。 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.
　スパッタリングガスに由来する原子は、詳しくは後述するが、スパッタリング法によって、金属層１を形成する場合に、金属層１に取り込まれる原子であり、スパッタリングガスに由来する原子として、具体的には、クリプトン原子および／またはキセノン原子が挙げられる。つまり、金属層１は、クリプトン原子および／またはキセノン原子を含む。 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.
　スパッタリングガスに由来する原子として、好ましくは、クリプトン原子またはキセノン原子、より好ましくは、クリプトン原子が挙げられる。 Examples of the atom derived from the sputtering gas include a krypton atom or a xenon atom, and more preferably a krypton atom.
　金属層１におけるスパッタリングガスに由来する原子の含有量は、例えば、０．５原子％以下であり、好ましくは、０．２原子％以下、より好ましくは、０．１原子％以下、さらに好ましくは、０．０５原子％以下、とりわけ好ましくは、０．０２原子％以下、特に好ましくは、０．０１原子％以下である。スパッタリングガスに由来する原子の含有量は、例えば、蛍光Ｘ線分析や、実施例に関して後述するラザフォード後方散乱分析（Ｒｕｔｈｅｒｆｏｒｄ　Ｂａｃｋｓｃａｔｔｅｒｉｎｇ　Ｓｐｅｃｔｒｏｍｅｔｒｙ、　略称ＲＢＳ）によって同定される。 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 by, for example, fluorescent X-ray analysis or Rutherford Backscattering Spectrum (abbreviated as RBS), which will be described later with reference to Examples.
　上記含有量の下限は、蛍光Ｘ線分析装置またはラザフォード後方散乱分析により、クリプトン原子および／またはキセノン原子の存在を確認できたときに対応する割合であり、少なくとも、０．００００１原子％以上である。 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. ..
　金属層１の厚みは、例えば、１０ｎｍ以上、好ましくは、３０ｎｍ以上であり、また、例えば、５０００ｎｍ以下、好ましくは、１５００ｎｍ以下、より好ましくは、５００ｎｍ以下、さらに好ましくは、３００ｎｍ以下、とりわけ好ましくは、１００ｎｍ以下である。 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.
　金属層１の厚みの測定方法は、後述する実施例において詳述する。 The method for measuring the thickness of the metal layer 1 will be described in detail in Examples described later.
　次に、金属層１の製造方法について、図２Ａおよび図２Ｂを参照して、説明する。 Next, the method for manufacturing the metal layer 1 will be described with reference to FIGS. 2A and 2B.
　この製造方法では、スパッタリングガス（クリプトンおよび／またはキセノン）存在下において、上記金属（主成分として、第３周期および／または第４周期に属する金属を含む金属）をターゲットとするスパッタリング法によって、金属層１を形成する。 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.
　スパッタリング法によって、金属層１を形成するには、まず、図２Ａに示すように、基材２を準備する。 To form the metal layer 1 by the sputtering method, first, as shown in FIG. 2A, the base material 2 is prepared.
　基材２は、フィルム形状を有する。 The base material 2 has a film shape.
　基材２としては、例えば、可撓性の観点から、高分子フィルムが挙げられる。高分子フィルムの材料としては、例えば、ポリエチレン、ポリプロピレン、シクロオレフィンポリマーなどのオレフィン樹脂、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート、ポリエチレンナフタレートなどのポリエステル樹脂、例えば、ポリメタクリレートなどの（メタ）アクリル樹脂（アクリル樹脂および／またはメタクリル樹脂）、例えば、ポリカーボネート樹脂、ポリエーテルスルフォン樹脂、ポリアリレート樹脂、メラミン樹脂、ポリアミド樹脂、ポリイミド樹脂、セルロース樹脂、ポリスチレン樹脂などが挙げられ、好ましくは、ポリエステル樹脂、より好ましくは、ポリエチレンテレフタレート（ＰＥＴ）が挙げられる。 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, and polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate and polyethylene naphthalate, and (meth) such as polymethacrylate. ) Acrylic resin (acrylic resin and / or methacrylic resin), for example, polycarbonate resin, polyether sulfone 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.
　基材２の厚みは、例えば、１μｍ以上、好ましくは、１０μｍ以上、好ましくは、３０μｍ以上であり、また、例えば、３００μｍ以下、好ましくは、２００μｍ以下、より好ましくは、１００μｍ以下、さらに好ましくは、６０μｍ以下である。 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.
　基材２の厚みは、ダイヤルゲージ（ＰＥＡＣＯＣＫ社製、「ＤＧ－２０５」）を用いて測定できる。 The thickness of the base material 2 can be measured using a dial gauge ("DG-205" manufactured by PEACOCK).
　また、基材２には、必要により、耐擦傷性を付与する観点から、ハードコート処理などの表面処理を施すことができる。 Further, the base material 2 can be subjected to a surface treatment such as a hard coat treatment from the viewpoint of imparting scratch resistance, if necessary.
　次いで、図２Ｂに示すように、スパッタリングガス（クリプトンおよび／またはキセノン）存在下において、上記金属をターゲットとするスパッタリング法によって、基材２の厚み方向一方面に、金属層１を形成（配置）する。 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.
　具体的には、スパッタリング装置において、基材２を成膜ロールの周面に沿って搬送しつつ、上記金属からなるターゲットに、基材２の厚み方向一方面を対向させながら、スパッタリングガス（好ましくは、クリプトンまたはキセノン、より好ましくは、クリプトン）の存在下、スパッタリングする。 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).
　スパッタリングとしては、例えば、２極スパッタリング法、ＥＣＲ（電子サイクロトロン共鳴）スパッタリング法、マグネトロンスパッタリング法、イオンビームスパッタリング法などが挙げられる。 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.
　また、スパッタリングにおいて、クリプトンおよび／またはキセノン以外に、例えば、酸素などの反応性ガスを存在させることもできる。 Further, in sputtering, a reactive gas such as oxygen can be present in addition to krypton and / or xenon.
　スパッタリング装置内におけるクリプトンおよび／またはキセノンの分圧は、例えば、０．０１Ｐａ以上、好ましくは、０．１Ｐａ以上、より好ましくは、０．３Ｐａ以上であり、また、例えば、１０Ｐａ以下、好ましくは、５Ｐａ以下、より好ましくは、１Ｐａ以下である。 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.
　スパッタリング装置内における圧力（成膜圧力）は、クリプトンおよび／またはキセノンの分圧、および、反応性ガスの分圧の合計圧力であり、例えば、０．１Ｐａ以上、好ましくは、０．３Ｐａ以上であり、また、例えば、１５Ｐａ以下、好ましくは、１０Ｐａ以下、より好ましくは、５Ｐａ以下、さらに好ましくは、１Ｐａ以下、とりわけ好ましくは、０．５Ｐａ以下である。 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.
　また、スパッタリングに用いる電源としては、例えば、直流（ＤＣ）電源、交流中周波（ＡＣ／ＭＦ）電源、高周波（ＲＦ）電源、直流電源を重畳した高周波電源が挙げられ、好ましくは、直流（ＤＣ）電源が挙げられる。 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.
　ターゲット表面の水平磁場の強度は、例えば、１０ｍＴ以上、好ましくは、２０ｍＴ以上であり、また、例えば、２００ｍＴ以下、好ましくは、１００ｍＴ以下である。ターゲット表面の水平磁場の強度を前記範囲に調整することにより、金属層１におけるスパッタリングガスの原子含有量を調整することができる。 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 surface of the target within the above range, the atomic content of the sputtering gas in the metal layer 1 can be adjusted.
　成膜ロールの温度は、例えば、－３０℃以上、好ましくは、－１０℃以上であり、また、例えば、１８０℃以下、好ましくは、９０℃以下、より好ましくは、６０℃以下、さらに好ましくは、４０℃以下、とりわけ好ましくは、１０℃未満である。 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.
　上記のスパッタリングにより、金属層１が、基材２の厚み方向一方面に形成（配置）される。これにより、金属層１が得られるとともに、基材２と金属層１とを厚み方向一方側に向かって順に備える積層体３が得られる。 By the above sputtering, the metal layer 1 is formed (arranged) on one side 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.
　そして、このような金属層１は、導電性を有する。 And, such a metal layer 1 has conductivity.
　金属層１が、導電性を有すると、後述するタッチセンサ、調光素子、光電変換素子、熱線制御部材、アンテナ、電磁波シールド部材、画像表示装置などに備えられる電極部材として、好適に用いることができる。 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.
　詳しくは、金属層１の表面抵抗値は、金属が銅（Ｃｕ）からなる場合には、例えば、５Ω／□以下、好ましくは、０．５Ω／□以下、より好ましくは、０．３５Ω／□以下、さらに好ましくは、０．３０Ω／□以下、ことさらに好ましくは、０．２３Ω／□以下であり、また、通常、０．００１Ω／□超過、また、０．０１Ω／□以上、好ましくは、０．１Ω／□以上である。 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.
　また、金属層１の表面抵抗値は、金属がアルミニウム（Ａｌ）からなる場合には、例えば、１０Ω／□以下、好ましくは、５．００Ω／□以下、より好ましくは、２．００Ω／□以下、さらに好ましくは、１．７０Ω／□以下であり、また、通常、０．００１Ω／□超過、また、０．１Ω／□以上、好ましくは、１．００Ω／□以上である。 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.
　なお、表面抵抗値は、ＪＩＳ　Ｋ７１９４に準拠して、４端子法により測定できる。 The surface resistance value can be measured by the 4-terminal method in accordance with JIS K7194.
　また、金属層１の比抵抗は、金属が銅（Ｃｕ）からなる場合には、例えば、１０×１０－６Ω・ｃｍ以下、好ましくは、２．５０×１０－６Ω・ｃｍ以下、より好ましくは、２．４０×１０－６Ω・ｃｍ以下、さらに好ましくは、２．３０×１０－６Ω・ｃｍ以下、とりわけ好ましくは、２．０５×１０－６Ω・ｃｍ以下であり、また、例えば、０．１０×１０－６Ω・ｃｍ以上である。 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.
　また、金属層１の比抵抗は、金属がアルミニウム（Ａｌ）からなる場合には、例えば、２０×１０－６Ω・ｃｍ以下、好ましくは、９．０×１０－６Ω・ｃｍ以下、より好ましくは、７．０×１０－６Ω・ｃｍ以下であり、また、例えば、０．１０×１０－６Ω・ｃｍ以上、好ましくは、１．０×１０－６Ω・ｃｍ以上である。 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.
　なお、比抵抗は、ＪＩＳ　Ｋ７１９４に準拠して、４端子法により求めた表面抵抗値と、金属層１の厚みとを用いて、下記式（１）に基づき、算出できる。 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.
　金属層１の比抵抗＝金属層１の厚み×金属層１の表面抵抗値　　（１）
　また、上記のスパッタリング法によって、金属層１を製造すると、スパッタリングガスに由来する原子が金属層１に取り込まれる。 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.
　しかし、この方法では、スパッタリングガスとして、通常用いられるアルゴンに代えて、アルゴンよりも原子量の大きいクリプトンおよび／またはキセノンを用いるため、スパッタリングガスに由来する原子が金属層１に取り込まれることを抑制できる。 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. ..
　つまり、このような金属層１は、クリプトン原子および／またはキセノン原子を含むものの、上記したように、クリプトン原子および／またはキセノン原子が取り込まれている量は抑制されているため、この金属層１は、加熱前後において、抵抗値の増加を抑制できる（換言すれば、この金属層１は、加熱安定性に優れる。）。 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).
　また、このような金属層１は、主成分として、第３周期および／または第４周期に属する金属を含みながら、上記したように、加熱安定性に優れる。つまり、この方法によれば、例えば、金（Ａｕ）（第６周期に属する金属）などの高価な金属を主成分としなくても、加熱安定性に優れる金属層１を製造できる。そのため、工業生産性に優れる。 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.
　金属層１は、基材２とは反対の側に、金属層１と隣接する樹脂層（図示しない）を備えていても良い。樹脂層は、例えば、金属層１と他の部材とを貼り合せるための接着層や粘着層であり、また、例えば、金属層１を保護するコート層である。樹脂層の材料に限定はなく、アクリル樹脂などの公知の樹脂を用いることができる。また、樹脂層には、紫外線吸収剤や腐食防止剤を含有していても良い。紫外線吸収剤や腐食防止剤の材料に限定はないが、たとえな、特開２０１５－０２２３９７に開示されるベンゾトリアゾール系化合物などが挙げられる。 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.
　また、図３に示すように、積層体３において、金属層１をパターン化することもできる。つまり、金属層１は、パターン形状を有する。 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.
　金属層１をパターン化するには、例えば、金属層１を、エッチングする。これによって、積層体３は、金属層１を有するパターン部４と、金属層１を有していない非パターン部５とを有する。積層体３は、パターン部４と非パターン部５の上面に、樹脂層（図示しない）を備えていても良い。樹脂層は、例えば、積層体３と他の部材とを貼り合せるための接着層や粘着層であり、また、例えば、積層体３のパターン部４を保護するコート層である。また、樹脂層には、紫外線吸収剤や腐食防止剤、マイグレーション防止剤を含有していても良く、例えば、特開２０１５－０２２３９７に開示されるベンゾトリアゾール系化合物などを含有することができる。 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 Japanese Patent Application Laid-Open No. 2015-0222397.
　そして、この金属層１は、種々の用途に用いられ、例えば、タッチセンサ、調光素子（ＰＤＬＣ、ＰＮＬＣやＳＰＤなどの電圧駆動型調光素子やエレクトロクロミック（ＥＣ）などの電流駆動型調光素子）、光電変換素子（有機薄膜太陽電池や色素増感太陽電池に代表される太陽電池素子）、熱線制御部材（近赤外反射および／または吸収部材や遠赤外反射および／または吸収部材）、アンテナ（光透過性アンテナ）、電磁波シールド部材、ヒーター部材、画像表示装置などに備えられる電極部材として好適に用いられる。 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, or the like.
　このようなタッチセンサ、調光素子、光電変換素子、熱線制御部材、アンテナ、電磁波シールド部材、ヒーター部材、および、画像表示装置は、本発明の金属層１を備えるため、加熱安定性に優れる。 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.
　以下の記載において用いられる配合割合（含有割合）、物性値、パラメータなどの具体的数値は、上記の「発明を実施するための形態」において記載されている、それらに対応する配合割合（含有割合）、物性値、パラメータなど該当記載の上限値（「以下」、「未満」として定義されている数値）または下限値（「以上」、「超過」として定義されている数値）に代替することができる。また、以下の記載において特に言及がない限り、「部」および「％」は質量基準である。 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．金属層の製造
　　実施例１
　ＰＥＴフィルムロール（東レ社製、厚み５０μｍ）からなる基材の厚み方向一方面に、アクリル樹脂からなる紫外線硬化性樹脂を塗布し、紫外線照射により硬化させた。これにより、厚み２μｍのハードコート層を形成し、基材を準備した。 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.
　この基材を、真空スパッタ装置に設置して、到達真空度が０．９×１０－４Ｐａとなるよう十分に真空排気し、基材を脱ガス処理した。その後、基材を成膜ロールに沿うように搬送しながら、クリプトン原子（スパッタリングガス）が存在する低圧環境下において、銅（Ｃｕ）をターゲットとするスパッタリング法によって、基材の厚み方向一方面に、厚み７０ｎｍの金属層を形成（配置）した。これにより、金属層を製造した。なお、スパッタリングの条件は、以下の通りである。
＜スパッタリングの条件＞
電源：ＤＣ電源
ターゲットの水平磁場強度：９０ｍＴ
成膜気圧：０．４Ｐａ
成膜ロール温度：－８℃ 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
　　実施例２
　金属層の厚みを８７ｎｍに変更した以外は、実施例１と同様にして、金属層を製造した。 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.
　　実施例３
　ターゲットをアルミニウム（Ａｌ）に変更し、ターゲットの水平磁場強度を５０ｍＴに変更した以外は、実施例１と同様にして、金属層を製造した。 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.
　　比較例１
　スパッタリングガスをアルゴンガスに変更した以外は、実施例１と同様にして、金属層を製造した。 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.
　　比較例２
　スパッタリングガスをアルゴンガスに変更した以外は、実施例２と同様にして、金属層を製造した。 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.
　　比較例３
　スパッタリングガスをアルゴンガスに変更した以外は、実施例３と同様にして、金属層を製造した。 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．評価
　＜金属層の厚み＞
　各実施例および各比較例の金属層について、ＦＩＢマイクロサンプリング法により、ＦＩＢ装置（Ｈｉｔａｃｈｉ製、「ＦＢ２２００」、加速電圧：１０ｋＶ）を用いて、ＴＥＭ用断面試料を作製した。次いで、電界放射型透過電子顕微鏡（ＦＥ－ＴＥＭ、ＪＯＥＬ社製、「ＪＥＭ－２８００」、加速電圧：２００ｋＶ）を用いて断面観察して、金属層の厚みを測定した。その結果を表１に示す。 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.
　＜表面抵抗値の測定＞
　各実施例および各比較例の金属層について、ＪＩＳ　Ｋ７１９４に準拠して、４端子法により、表面抵抗値（以下、表面抵抗値Ａと称する。）を測定した。その結果を表１に示す。 <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.
　次いで、各実施例および各比較例の金属層を、８０℃、３時間加熱し、同様の方法で、表面抵抗値（以下、表面抵抗値Ｂと称する。）を測定した。その結果を表１に示す。 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.
　別途、各実施例および各比較例の金属層を、１４０℃、１時間加熱し、同様の方法で、表面抵抗値（以下、表面抵抗値Ｃと称する。）を測定した。その結果を表１に示す。
＜加熱安定性＞
　各実施例および各比較例の金属層について、加熱安定性を評価した。 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.
　具体的には、下記式（２）および下記式（３）に基づき、抵抗変化の比（Ｂ／Ａ）および抵抗変化の比（Ｃ／Ａ）を算出した。 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).
　抵抗変化の比（Ｂ／Ａ）＝表面抵抗値Ｂ／表面抵抗値Ａ　　（２）
　抵抗変化の比（Ｃ／Ａ）＝表面抵抗値Ｃ／表面抵抗値Ａ　　（３）
　抵抗変化の比（Ｂ／Ａ）および抵抗変化の比（Ｃ／Ａ）は、加熱前の表面抵抗値に対する加熱後の表面抵抗値の変化を示しており、抵抗変化の比（Ｂ／Ａ）および抵抗変化の比（Ｃ／Ａ）が小さければ、加熱前後において、金属層の抵抗値の増加を抑制できること（加熱安定性に優れること）を意味する。 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).
　＜比抵抗の測定＞
　各実施例および各比較例の金属層について、下記式（４）に基づき、比抵抗を算出した。 <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).
　金属層の比抵抗＝金属層の厚み×金属層の表面抵抗値Ａ　　（４）
　＜クリプトン原子およびアルゴン原子の同定＞
　各実施例および各比較例の金属層に含有されるクリプトン原子およびアルゴン原子の存否を、ラザフォード後方散乱分光法（ＲＢＳ）によって分析した。検出元素である、金属元素（ＣｕもしくはＡｌ）、Ａｒ、Ｋｒの３元素に関して、元素比率を求めることにより、金属層におけるクリプトン原子またはアルゴン原子の存否を求めた。評価の結果、実施例１～３の金属層についてはクリプトン原子が、また、比較例１～３の金属層についてはアルゴン原子が、含有されていることを確認した。
＜使用装置＞
　Ｐｅｌｌｅｔｒｏｎ　３ＳＤＨ（Ｎａｔｉｏｎａｌ　Ｅｌｅｃｔｒｏｓｔａｔｉｃｓ　Ｃｏｒｐｏｒａｔｉｏｎ製）
＜測定条件＞
　入射イオン：４Ｈｅ＋＋
　入射エネルギー：２３００ｋｅＶ
　入射角：０ｄｅｇ
　散乱角：１６０ｄｅｇ
　試料電流：５ｎＡ
　ビーム径：２ｍｍφ
　面内回転：無
　照射量：７５μＣ 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．考察
　実施例１および比較例１では、スパッタリングガスが異なる以外、同様の手順で、金属層を製造している。 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.
　スパッタリングガスとして、クリプトンを用いる実施例１は、アルゴンを用いる比較例１に比べて、抵抗変化の比（Ｂ／Ａ）および抵抗変化の比（Ｃ／Ａ）が小さい。 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.
　このことから、スパッタリングガスとして、クリプトンを用いれば、加熱安定性に優れることがわかる。 From this, it can be seen that if krypton is used as the sputtering gas, the heating stability is excellent.
　また、このことは、実施例２と比較例２との比較、および、実施例３と比較例３との比較においても同様である。 This also applies to the comparison between Example 2 and Comparative Example 2 and the comparison between Example 3 and Comparative Example 3.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　なお、上記発明は、本発明の例示の実施形態として提供したが、これは単なる例示にすぎず、限定的に解釈してはならない。当該技術分野の当業者によって明らかな本発明の変形例は、後記請求の範囲に含まれるものである。 Although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an example and should not be construed in a limited manner. Modifications of the invention that are apparent to those skilled in the art are within the scope of the claims.
　金属層、タッチセンサ、調光素子、光電変換素子、熱線制御部材、アンテナ、電磁波シールド部材、画像表示装置および金属層の製造方法は、例えば、タッチパネルなどの電極部材として、好適に用いられる。 The method for manufacturing 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 metal layer is suitably used as an electrode member such as a touch panel, for example.
　１　　　金属層 1 Metal layer

Claims (11)

  1. 　主成分として、第３周期および／または第４周期に属する金属を含み、かつ、
    　クリプトン原子および／またはキセノン原子を含むことを特徴とする、金属層。     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.
  2. 　導電性を有することを特徴とする、請求項１に記載の金属層。 The metal layer according to claim 1, which is characterized by having conductivity.
  3. 　パターン形状を有することを特徴とする、請求項１に記載の金属層。 The metal layer according to claim 1, characterized by having a pattern shape.
  4. 　請求項１に記載の金属層を備えることを特徴とする、タッチセンサ。 A touch sensor comprising the metal layer according to claim 1.
  5. 　請求項１に記載の金属層を備えることを特徴とする、調光素子。 A dimming element comprising the metal layer according to claim 1.
  6. 　請求項１に記載の金属層を備えることを特徴とする、光電変換素子。 A photoelectric conversion element comprising the metal layer according to claim 1.
  7. 　請求項１に記載の金属層を備えることを特徴とする、熱線制御部材。 A heat ray control member comprising the metal layer according to claim 1.
  8. 　請求項１に記載の金属層を備えることを特徴とする、アンテナ。 An antenna comprising the metal layer according to claim 1.
  9. 　請求項１に記載の金属層を備えることを特徴とする、電磁波シールド部材。 An electromagnetic wave shielding member comprising the metal layer according to claim 1.
  10. 　請求項１に記載の金属層を備えることを特徴とする、画像表示装置。 An image display device comprising the metal layer according to claim 1.
  11. 　クリプトンおよび／またはキセノン存在下において、第３周期および／または第４周期に属する金属をターゲットとするスパッタリング法によって、金属層を形成することを特徴とする、金属層の製造方法。 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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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH021918A (en) * 1988-06-10 1990-01-08 Fujitsu Ltd Manufacture of semiconductor device
JPH0459964A (en) * 1990-06-27 1992-02-26 Nec Home Electron Ltd Production of thin aluminum alloy film
JPH05263226A (en) * 1992-03-17 1993-10-12 Fujitsu Ltd Thin film forming method
JPH07258827A (en) * 1994-03-25 1995-10-09 Mitsubishi Electric Corp Thin metallic film and its formation and semiconductor device and its production
JPH09306918A (en) * 1996-05-16 1997-11-28 Sony Corp Barrier metal forming method in forming process of solder ball bump
JP2005019338A (en) * 2003-06-27 2005-01-20 Tadahiro Omi Organic electroluminescent device, its manufacturing method, and display device
JP2006161120A (en) * 2004-12-09 2006-06-22 Ulvac Japan Ltd Deposition method of heusler's alloy film, and tunnelling magnetoresistive element
JP2007250430A (en) * 2006-03-17 2007-09-27 Sumitomo Metal Mining Co Ltd Transparent conductive thin film and transparent conductive film using same
JP2008149681A (en) * 2006-12-20 2008-07-03 Fujifilm Corp Translucent conductive material
WO2015125558A1 (en) * 2014-02-20 2015-08-27 コニカミノルタ株式会社 Method for manufacturing transparent electroconductive body and electroconductive body

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5914036B2 (en) 2011-04-20 2016-05-11 日東電工株式会社 Method for producing conductive laminated film

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH021918A (en) * 1988-06-10 1990-01-08 Fujitsu Ltd Manufacture of semiconductor device
JPH0459964A (en) * 1990-06-27 1992-02-26 Nec Home Electron Ltd Production of thin aluminum alloy film
JPH05263226A (en) * 1992-03-17 1993-10-12 Fujitsu Ltd Thin film forming method
JPH07258827A (en) * 1994-03-25 1995-10-09 Mitsubishi Electric Corp Thin metallic film and its formation and semiconductor device and its production
JPH09306918A (en) * 1996-05-16 1997-11-28 Sony Corp Barrier metal forming method in forming process of solder ball bump
JP2005019338A (en) * 2003-06-27 2005-01-20 Tadahiro Omi Organic electroluminescent device, its manufacturing method, and display device
JP2006161120A (en) * 2004-12-09 2006-06-22 Ulvac Japan Ltd Deposition method of heusler's alloy film, and tunnelling magnetoresistive element
JP2007250430A (en) * 2006-03-17 2007-09-27 Sumitomo Metal Mining Co Ltd Transparent conductive thin film and transparent conductive film using same
JP2008149681A (en) * 2006-12-20 2008-07-03 Fujifilm Corp Translucent conductive material
WO2015125558A1 (en) * 2014-02-20 2015-08-27 コニカミノルタ株式会社 Method for manufacturing transparent electroconductive body and electroconductive body

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