CN117043888A - Transparent conductive layer, transparent conductive film, and article - Google Patents

Transparent conductive layer, transparent conductive film, and article Download PDF

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Publication number
CN117043888A
CN117043888A CN202280022825.6A CN202280022825A CN117043888A CN 117043888 A CN117043888 A CN 117043888A CN 202280022825 A CN202280022825 A CN 202280022825A CN 117043888 A CN117043888 A CN 117043888A
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transparent conductive
conductive layer
less
region
thickness
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藤野望
鸦田泰介
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Nitto Denko Corp
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Nitto Denko Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials Engineering (AREA)
  • Non-Insulated Conductors (AREA)
  • Laminated Bodies (AREA)

Abstract

The transparent conductive layer (1) comprises: an inorganic oxide containing a rare gas having an atomic number larger than that of argon. Integrated intensity I of peak at (440) plane when X-ray diffraction is performed on transparent conductive layer (1) 440 Integrated intensity I of peak relative to (222) plane 222 Ratio (I) 440 /I 222 ) Less than 0.130.

Description

Transparent conductive layer, transparent conductive film, and article
Technical Field
The present invention relates to a transparent conductive layer, a transparent conductive film, and an article.
Background
Transparent conductive layers on film substrates are known (for example, see patent document 1 below). The transparent conductive layer described in patent document 1 is crystalline. The transparent conductive layer is arranged on the article. The article includes a touch panel.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2014-157814
Disclosure of Invention
Problems to be solved by the invention
Depending on the type, purpose and purpose of the article, the method for producing the article may include a heating step. The temperature of the heating step is, for example, 100 ℃ to 150 ℃. In this case, the transparent conductive layer is required to be capable of suppressing an increase in surface resistance even after the heating step in the method for producing an article. That is, the transparent conductive layer is required to have excellent heat resistance.
However, the transparent conductive layer described in patent document 1 has a drawback that the above requirements cannot be satisfied sufficiently.
The invention provides a transparent conductive layer, a transparent conductive film and an article, which can inhibit the increase of surface resistance even through a heating process in the manufacturing method of the article.
Solution for solving the problem
The invention (1) comprises a transparent conductive layer comprising an inorganic oxide containing a rare gas having an atomic number greater than that of argon, wherein the transparent conductive layer has an integrated intensity I of a peak of a (440) plane when subjected to X-ray diffraction 440 Integrated intensity I of peak relative to (222) plane 222 Ratio (I) 440 /I 222 ) Less than 0.130.
The transparent conductive layer according to the invention (2) comprises the transparent conductive layer according to the item (1), and the thickness thereof is less than 150nm.
The invention (3) comprises the transparent conductive layer according to (1) or (2), wherein the inorganic oxide is an indium tin composite oxide.
The invention (4) comprises a transparent conductive film, which comprises, in order from one side in the thickness direction: a substrate comprising a resin, and the transparent conductive layer according to any one of (1) to (3).
The invention (5) comprises an article comprising the transparent conductive layer according to any one of (1) to (3).
The invention (6) comprises an article comprising the transparent conductive film according to (4).
ADVANTAGEOUS EFFECTS OF INVENTION
The transparent conductive layer and the transparent conductive film of the present invention can suppress an increase in surface resistance even in a heating step in a method for manufacturing an article.
Drawings
Fig. 1 is a cross-sectional view of an embodiment of a transparent conductive layer of the present invention.
Fig. 2 is a cross-sectional view of a transparent conductive film including the transparent conductive layer shown in fig. 1.
Fig. 3 is a graph showing the relationship between the oxygen introduction amount and the resistivity in the reactive sputtering of example 1.
Detailed Description
1. One embodiment of the transparent conductive layer
A transparent conductive layer 1 as an embodiment of the present invention will be described with reference to fig. 1. The transparent conductive layer 1 extends in the planar direction. The plane direction is orthogonal to the thickness direction. The transparent conductive layer 1 is crystalline.
1.1 inorganic oxide contained in transparent conductive layer
The transparent conductive layer 1 contains an inorganic oxide. Examples of the inorganic oxide include metal oxides. The metal oxide comprises at least 1 metal selected from the group consisting of In, sn, zn, ga, sb, nb, ti, si, zr, mg, al, au, ag, cu, pd, W. Specifically, as a material of the transparent conductive layer 1, indium zinc composite oxide (IZO), indium gallium zinc composite oxide (IGZO), indium gallium composite oxide (IGO), indium tin composite oxide (ITO), and antimony tin composite oxide (ATO) are preferable, and indium tin composite oxide (ITO) is preferable from the viewpoint of improving heat resistance.
1.2 tin oxide (SnO) 2 ) Content of (3)
Tin oxide (SnO) in indium tin composite oxide 2 ) The content of (C) is, for example, 0.5 mass% or more, preferably 3 mass% or more, more preferably 4 mass%The amount is preferably not less than 5% by mass, more preferably not less than 6% by mass, and further, for example, less than 50% by mass, preferably not more than 25% by mass, more preferably not more than 15% by mass, more preferably not more than 10% by mass. When the content of tin oxide is not less than the lower limit, the ratio (I 440 /I 222 ) Is set to a desired range. The tin oxide content may be, for example, tin oxide (SnO) in a sintered body (target) of a mixture of indium oxide and tin oxide 2 ) Is determined by the content of (3). Further, for example, the transparent conductive layer 1 may be determined by analysis by XPS (X-ray photoelectron spectroscopy ). If necessary, tin oxide (SnO) in the thickness direction of the transparent conductive layer 1 can be obtained by obtaining depth profile of XPS 2 ) Is contained in the composition.
1.2.1 distribution of tin oxide content
The content of tin oxide in the indium tin composite oxide may be distributed in the thickness direction. As shown in the enlarged view of fig. 1, in the present embodiment, the transparent conductive layer 1 includes, in order from one side in the thickness direction, a 1 st region 3 and a 2 nd region 4 in which the tin oxide content is different from each other. That is, in the present embodiment, the 2 nd region 4 is arranged on one side of the 1 st region 3 in the thickness direction. The content C1 of tin oxide in the 1 st region 3 is, for example, higher than the content C2 of tin oxide in the 2 nd region 4. The ratio (C1/C2) of the content C1 of tin oxide in the 1 st region 3 to the content C2 of tin oxide in the 2 nd region 4 is, for example, more than 1, preferably 1.5 or more, more preferably 2 or more, still more preferably 2.5 or more, particularly preferably 3 or more, and most preferably 3.3 or more. The ratio (C1/C2) is, for example, 100 or less, preferably 25 or less, and more preferably 10 or less. The boundaries of the 1 st region 3 and the 2 nd region 4 may not be clearly observed.
1.2.2 content of tin oxide in zone 1, 3
Specifically, the content C1 of tin oxide in the 1 st region 3 is, for example, 5 mass% or more, preferably 7 mass% or more, more preferably 9 mass% or more, and is, for example, 50 mass% or less, preferably 30 mass% or less, more preferably 25 mass% or less, more preferably 20 mass% or less.
1.2.3 content of tin oxide in zone 24
The content C1 of tin oxide in the 2 nd region 4 is, for example, 0.1 mass% or more, preferably 1 mass% or more, more preferably 2 mass% or more, and is, for example, 9 mass% or less, preferably 7 mass% or less, more preferably 5 mass% or less.
1.3 rare gas 2 having atomic number larger than that of argon contained in inorganic oxide
The inorganic oxide contains a rare gas 2 having an atomic number larger than that of argon. In the present embodiment, as shown in an enlarged view in fig. 1, a rare gas 2 having an atomic number larger than that of argon is present in the entire transparent conductive layer 1 in the thickness direction. Even if the transparent conductive layer 1 includes the 1 st region 3 and the 2 nd region 4, the rare gas 2 having an atomic number larger than that of argon exists in both the 1 st region 3 and the 2 nd region 4.
The transparent conductive layer 1 is a composition obtained by mixing an inorganic oxide (preferably, a metal oxide) with a rare gas 2 having an atomic number larger than that of argon.
Examples of the rare gas having an atomic number larger than that of argon include krypton, xenon, and radon. They may be used alone or in combination. The rare gas having an atomic number larger than that of argon is preferably krypton or xenon, and krypton (Kr) is more preferably used from the viewpoint of low cost and excellent electrical conductivity.
The method for identifying the rare gas having an atomic number larger than that of argon is not limited. For example, the rare gas having an atomic number larger than that of argon in the transparent conductive layer 1 is preferably identified (whether or not it is present) by rutherford backscattering analysis (Rutherford Backscattering Spectrometry), secondary ion mass spectrometry, laser resonance ionization mass spectrometry, and/or fluorescent X-ray analysis, and from the viewpoint of analysis easiness, the identification is preferably performed by fluorescent X-ray analysis. Details of the fluorescent X-ray analysis are set forth in the examples. In order to quantify a rare gas having an atomic number greater than argon, the rutherford backscattering analysis is performed, and therefore the determination cannot be performed because the content of the rare gas having an atomic number greater than argon is not equal to or greater than the detection threshold (lower limit), whereas when the fluorescent X-ray analysis is performed, if the presence of the rare gas having an atomic number greater than argon is identified, it is determined that the region in which the content of the rare gas having an atomic number greater than argon in the transparent conductive layer 1 is equal to or greater than 0.0001atom% is included.
The content ratio of the rare gas having an atomic number larger than that of argon in the inorganic oxide (transparent conductive layer 1) is, for example, 0.0001atom% or more, preferably 0.001atom% or more, and further, for example, 1.0atom% or less, more preferably 0.7atom% or less, still more preferably 0.5atom% or less, still more preferably 0.3atom% or less, particularly preferably 0.2atom% or less, and most preferably 0.15atom% or less. When the content ratio of the rare gas having an atomic number larger than that of argon in the inorganic oxide (transparent conductive layer 1) is in the above range, the heat resistance of the transparent conductive layer 1 can be improved.
In sputtering described later, when the sputtering gas contains argon, a large amount of argon enters the transparent conductive layer 1. In contrast, when the sputtering gas contains a rare gas having an atomic number larger than that of argon and does not contain argon, the transparent conductive layer 1 can suppress a large amount of the sputtering gas from entering. Therefore, the transparent conductive layer 1 becomes dense, and as a result, the heat resistance of the transparent conductive layer 1 is improved.
1.4 peak of plane (222) and plane (440) in X-ray diffraction
When X-ray diffraction is performed on the transparent conductive layer 1, peaks of the (222) plane and the (440) plane exist. (222) The peaks of the surface and the (440) surface are inherent peaks included in the spectrum obtained when the crystalline transparent conductive layer 1 is subjected to X-ray diffraction.
1.4.1 Integral intensity I of peak of (440) plane 440 Integrated intensity I of peak relative to (222) plane 222 Ratio (I) 440 /I 222 )
(440) Integral intensity I of peak of face 440 Integrated intensity I of peak relative to (222) plane 222 Ratio (I) 440 /I 222 ) Less than 0.130.
On the other hand, the integrated intensity I of the peak of the (440) plane 440 Integrated intensity I of peak relative to (222) plane 222 Ratio (I) 440 /I 222 ) When the amount is 0.130 or more, the heat resistance may be lowered. That is, if the method for manufacturing the article having the transparent conductive layer 1 includes a heating step, the surface resistance may be increased.
On the other hand, in the present invention, the integrated intensity I of the peak of the (440) plane 440 Integrated intensity I of peak relative to (222) plane 222 Ratio (I) 440 /I 222 ) Less than 0.130, the heat resistance can be improved. That is, when the transparent conductive layer 1 is placed under a high-temperature atmosphere, an increase in surface resistance can be reliably suppressed.
(440) Integral intensity I of peak of face 440 Integrated intensity I of peak relative to (222) plane 222 Ratio (I) 440 /I 222 ) For example, it is preferably 0.128 or less, more preferably 0.127 or less, still more preferably 0.126 or less, particularly preferably 0.125 or less, and further preferably 0.124 or less, still more preferably 0.123 or less.
The above ratio (I 440 /I 222 ) The method within the above range is not limited.
1.4.2 Integral intensity I of peak of (440) plane 440 Integrated intensity I of peak relative to (222) plane 222 Ratio (I) 440 /I 222 ) The determination of (2) is performed based on the description of examples below.
1.5 other physical Properties of transparent conductive layer 1
The crystal grain diameter of the transparent conductive layer 1 is, for example, 0.1 μm or more, preferably 0.3 μm or more, more preferably 0.5 μm or more, and still more preferably 0.6 or more. The crystal grain diameter of the transparent conductive layer 1 is, for example, 1 μm or less, preferably 0.9 μm or less, more preferably 0.8 μm or less, and still more preferably 0.7 μm or less. When the grain diameter is not less than the lower limit, the heat resistance is excellent. When the crystal grain diameter is not more than the upper limit, the transparent conductive layer 1 is less likely to crack even when the substrate 6 containing a flexible resin is used. The grain size was determined by FE-SEM observation. Details of the determination are described in the examples below.
The transparent conductive layer 1 has a thickness of, for example, 5nm or more, preferably 10nm or more, more preferably 15nm or more, still more preferably 20nm or more, still more preferably 22nm or more, and further, for example, 500nm or less, preferably 300nm or less, more preferably 250nm or less, still more preferably 200nm or less, still more preferably less than 150nm, still more preferably 140nm or less, particularly preferably 100nm or less, 80nm or less, 50nm or less, and 35nm or less. When the thickness of the transparent conductive layer 1 is in the upper and lower limits, a good crystalline film can be obtained, and the heat resistance is excellent.
The thickness of each of the 1 st region 3 and the 2 nd region 4 is, for example, 3nm or more, preferably 5nm or more, more preferably 7nm or more, and is, for example, 200nm or less, preferably 100nm or less, more preferably 50nm or less, more preferably 25nm or less, more preferably 20nm or less, and particularly preferably 15nm or less.
When the transparent conductive layer 1 includes the 1 st region 3 and the 2 nd region 4, the ratio of the thickness of the 1 st region 3 to the thickness of the 2 nd region 4 is, for example, 0.1 or more, preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.7 or more, and is, for example, 10 or less, preferably 5 or less, more preferably 3 or less, still more preferably 2 or less.
The total light transmittance of the transparent conductive layer 1 is, for example, 75% or more, preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. The upper limit of the total light transmittance of the transparent conductive layer 1 is not limited.
The upper limit of the total light transmittance of the transparent conductive layer 1 is, for example, 100%.
The resistivity of the transparent conductive layer 1 is, for example, 5.0X10 -4 Omega cm or less, preferably 3X 10 -4 Omega cm or less, and, for example, 0.1X10 -4 Omega cm or more, preferably 1.1X10 g -4 Omega cm or more. The resistivity was measured by the four terminal method.
1.6 transparent conductive film 5
Next, a transparent conductive film 5 including the transparent conductive layer 1 will be described with reference to fig. 2. The transparent conductive film 5 extends in the planar direction. The transparent conductive film 5 includes a base material 6 and a transparent conductive layer 1 in this order on one side in the thickness direction. That is, in the present embodiment, the base material 6 and the transparent conductive layer 1 are disposed in this order on one side in the thickness direction in the transparent conductive film 5. In the present embodiment, the transparent conductive film 5 preferably includes only the base material 6 and the transparent conductive layer 1.
1.7 substrate 6
In the present embodiment, the substrate 6 forms the other surface of the transparent conductive film 5 in the thickness direction. The base material 6 improves the mechanical strength of the transparent conductive film 5. The base material 6 extends in the planar direction. The base material 6 contains, for example, a resin. When the base material 6 contains a resin, a transparent conductive film 5 having both excellent heat resistance and flexibility can be obtained. The resin will be described later. In the present embodiment, the base material 6 is not adjacent to a glass plate (not shown). In the present embodiment, the other surface of the base material 6 in the thickness direction is not in contact with the glass plate.
1.7.1 layer formation of substrate 6
In the present embodiment, the base material 6 includes a base material sheet 61 and a functional layer 60 in this order in the thickness direction. In the present embodiment, the functional layer 60 is a single layer. The functional layer 60 is in contact with one surface of the base material sheet 61 in the thickness direction. The functional layer 60 is preferably a hard coat layer 62. In the present embodiment, the base material 6 preferably includes a base material sheet 61 and a hard coat layer 62 in this order on the other side in the thickness direction.
1.7.1.1 base sheet 61
The base sheet 61 has flexibility. As the base sheet 61, for example, a resin film is given. The resin in the resin film is not limited. Examples of the resin include polyester resins, acrylic resins, olefin resins, polycarbonate resins, polyethersulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, polystyrene resins, and norbornene resins. From the viewpoints of transparency and mechanical strength, polyester resins are preferable as the resin. Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, and PET is preferable.
The thickness of the base sheet 61 is preferably 1 μm or more, more preferably 10 μm or more, and still more preferably 30 μm or more. The thickness of the base sheet 61 is preferably 300 μm or less, more preferably 200 μm or less, still more preferably 150 μm or less, and particularly preferably 100 μm or less. The ratio of the thickness of the base sheet 61 to the thickness of the base 6 is, for example, 0% or more, preferably 50% or more, more preferably 80% or more, and is, for example, 99.99% or less, preferably 99% or less.
1.7.1.2 hard coat layer 62
The hard coat layer 62 makes it difficult for one face of the transparent conductive layer 1 in the thickness direction to be scratched. The hard coat layer 62 is in contact with one surface of the base material sheet 61 in the thickness direction. The hard coat layer 62 is formed of resin. Specifically, the hard coat layer 62 is, for example, a cured product layer of a curable composition containing a curable resin. Examples of the curable resin include an acrylic resin, a urethane resin, an amide resin, a silicone resin, an epoxy resin, and a melamine resin. The curable resin is preferably an acrylic resin. The thickness of the hard coat layer 62 is, for example, 0.1 μm or more, preferably 0.5 μm or more, and is, for example, 10 μm or less, preferably 3 μm or less. The ratio of the thickness of the hard coat layer 62 to the thickness of the base sheet 61 is, for example, 0.01 or more, preferably 0.02 or more, more preferably 0.03 or more, and is, for example, 0.20 or less, preferably 0.10 or less, more preferably 0.05 or less. The thickness of the hard coat layer 62 corresponds to the thickness of the functional layer 60.
1.7.2 thickness of substrate 6
The thickness of the base material 6 is, for example, 5 μm or more, preferably 10 μm or more, more preferably 25 μm or more, and is, for example, 500 μm or less, preferably 200 μm or less, more preferably 100 μm or less. The thickness of the base material 6 is the total thickness of the base material sheet 61 and the hard coat layer 62.
1.7.3 physical Properties of the substrate 6
The total light transmittance of the base material 6 is, for example, 75% or more, preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. The upper limit of the total light transmittance of the base material 6 is not limited. The upper limit of the total light transmittance of the base material 6 is, for example, 100% or less. The total light transmittance of the base material 6 was determined based on JIS K7375-2008. The total light transmittance of the following members was obtained by the same method as described above.
As the substrate 6, commercially available ones can be used.
1.8 transparent conductive layer 1
In the transparent conductive film 5 of the present embodiment, the transparent conductive layer 1 forms one surface of the transparent conductive film 5 in the thickness direction. The transparent conductive layer 1 is disposed on one surface of the base material 6 in the thickness direction. The transparent conductive layer 1 is in contact with one surface of the base material 6 in the thickness direction. That is, the other surface of the transparent conductive layer 1 in the thickness direction is in contact with the base material 6. In the present embodiment, the other surface of the transparent conductive layer 1 is in contact with one surface of the hard coat layer 62 (functional layer 60) in the thickness direction.
As shown in the enlarged view of fig. 1, when the transparent conductive layer 1 has the 1 st region 3 and the 2 nd region 4, the 1 st region 3 is preferably arranged on one surface of the base material 6 in the thickness direction. The 1 st region 3 is preferably in contact with one surface of the hard coat layer 62 (see fig. 2) in the thickness direction. As shown in the enlarged view of fig. 1 and the enlarged view of fig. 2, when the transparent conductive layer 1 has the 1 st region 3 and the 2 nd region 4, the transparent conductive film 5 includes, in order toward one side in the thickness direction: a base material sheet 61, a hard coat layer 62, a 1 st region 3 and a 2 nd region 4. That is, the 2 nd region 4 is arranged on the opposite side of the substrate 6 in the thickness direction with respect to the 1 st region 3.
1.9 thickness and other physical Properties of transparent conductive film 5
The thickness of the transparent conductive film 5 is, for example, 2 μm or more, preferably 20 μm or more, more preferably 30 μm or more, and is, for example, 300 μm or less, preferably 200 μm or less, more preferably 100 μm or less.
The total light transmittance of the transparent conductive film 5 is, for example, 75% or more, preferably 80% or more, and 100% or less.
1.10 method for producing transparent conductive film 5
In this method, for example, each layer is arranged by a roll-to-roll method.
Preparation of 1.10.1 substrate 6
First, a base material 6 is prepared. Specifically, the curable composition is applied to one surface of the base sheet 61. Thereafter, the curable resin in the curable composition is cured by heat or ultraviolet irradiation. Thereby, the hard coat layer 62 is formed on one surface of the base sheet 61. Thereby, the base material 6 is prepared.
Formation of 1.10.2 transparent conductive layer 1
Thereafter, the transparent conductive layer 1 is formed on one surface of the base material 6 in the thickness direction. Specifically, first, an amorphous transparent conductive layer is formed on one surface of the base material 6 in the thickness direction, and thereafter, the amorphous transparent conductive layer is converted into a crystalline form, whereby the transparent conductive layer 1 is formed.
Formation of 1.10.2.1 amorphous transparent conductive layer
In order to form the amorphous transparent conductive layer, for example, sputtering is preferably performed, and reactive sputtering is preferably performed. Further, as sputtering, magnetron sputtering can be mentioned. More preferably, the sputtering is reactive magnetron sputtering.
In sputtering, a sputtering apparatus can be used. The sputtering apparatus includes a single film forming roller and a plurality of film forming chambers.
The film forming roller is provided with a temperature adjusting device. The temperature adjusting device can adjust the temperature of the film forming roller. The film-forming roller may be in contact with the substrate 6, and thus the temperature of the substrate 6 may be adjusted. The surface temperature of the film forming roller corresponds to the film forming temperature during sputtering. The film formation temperature is, for example, -50℃or higher, preferably-30℃or higher, more preferably-20℃or higher, still more preferably-10℃or higher, and, for example, 20℃or lower, preferably 10℃or lower, more preferably 5℃or lower, still more preferably 0℃or lower.
Each of the plurality of film forming chambers can supply sputtering gas to the inside. The sputtering gas includes a rare gas having an atomic number larger than that of argon. Examples of the rare gas having an atomic number larger than that of argon include krypton, xenon, and radon, and krypton (Kr) is preferable. The sputtering gas is preferably argon free.
The sputtering gas supplied to each of the plurality of film forming chambers is, for example, the same, and, for example, the sputtering gas supplied to one film forming chamber is a rare gas having an atomic number larger than that of argon, and the sputtering gas supplied to the other film forming chamber is argon. Preferably, the sputtering gas supplied to each of the plurality of film forming chambers is the same.
The sputtering gas is preferably mixed with a reactive gas. As the reactive gas, for example, oxygen may be mentioned. The ratio of the amount of the reactive gas to be introduced to the total amount of the sputtering gas and the reactive gas is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, and is, for example, 5.0% by mass or less, preferably 3.5% by mass or less.
The target is, for example, (a sintered body of) the above metal oxide. A plurality of targets are disposed in each of the plurality of film forming chambers. For example, the 1 st target is disposed in the 1 st film formation chamber. The 2 nd target is disposed in the 2 nd film forming chamber.
The 1 st target is (a sintered body of) a metal oxide corresponding to the 1 st region 3, and has the above (high) content of tin oxide.
The 2 nd film forming chamber is disposed downstream of the 1 st film forming chamber in the transport direction of the substrate 6. The 2 nd target is (a sintered body of) a metal oxide corresponding to the 2 nd region 4, and has the above-mentioned (low) content of tin oxide.
As shown in the enlarged view of fig. 1, in order to provide the transparent conductive layer 1 with the 1 st region 3 and the 2 nd region 4, the 1 st sputtering step is performed in the 1 st film forming chamber, and the 2 nd sputtering step is performed in the 2 nd film forming chamber.
The air pressure in the sputtering apparatus is, for example, 1.0Pa or less, and is, for example, 0.01Pa or more.
Thus, a laminate comprising the base material 6 and the amorphous transparent conductive layer was produced. In the case where the sputtering apparatus includes the 1 st and 2 nd film forming chambers, the amorphous transparent conductive layer includes the 1 st region 3 and the 2 nd region 4.
Conversion of 1.10.2.2 amorphous transparent conductive layer to crystalline
Thereafter, the amorphous transparent conductive layer is converted into a crystalline form, thereby forming the transparent conductive layer 1.
In order to convert the transparent conductive layer 1 into a crystalline form, an amorphous transparent conductive layer (a laminate including an amorphous transparent conductive layer) is heated.
The heating temperature is, for example, 80℃or higher, preferably 110℃or higher, more preferably 130℃or higher, particularly preferably 150℃or higher, and is, for example, 200℃or lower, preferably 180℃or lower, more preferably 175℃or lower, more preferably 170℃or lower. The heating time is, for example, 1 minute or more, preferably 3 minutes or more, more preferably 5 minutes or more, and, for example, 5 hours or less, preferably 3 hours or less, more preferably 2 hours or less. The heating is performed, for example, under vacuum, or under atmospheric air. From the viewpoint of improving heat resistance, it is preferable to perform heating under vacuum.
Alternatively, the transparent conductive film 5 having the amorphous transparent conductive layer may be left to stand at 20 ℃ or higher and lower than 80 ℃ for, for example, 10 hours or longer, preferably 24 hours or longer under the atmosphere, whereby the amorphous transparent conductive layer is converted into a crystalline state.
1.11 use of transparent conductive film 5
The transparent conductive layer 1 and/or the transparent conductive film 5 are used for an article. Examples of the article include an optical article. Specifically, examples of the article include a touch sensor, an electromagnetic wave shield, a solar cell, a light control element, a photoelectric conversion element, a heat ray control member, a translucent antenna member, a translucent heater member, an image display device, and illumination.
2. Effects of one embodiment
With respect to the transparent conductive layer 1 and the transparent conductive film 5, even if the manufacturing process of the article includes a heating process, an increase in surface resistance can be suppressed. Therefore, the article provided with the transparent conductive layer 1 and/or the transparent conductive film 5 is excellent in heat resistance.
In particular, the solar cell, the light control element, the heat ray control member, and the light transmissive heater member are manufactured by a method including a severe heating step in which the temperature is easily increased. However, since each article includes the transparent conductive layer 1 and/or the transparent conductive film 5, an increase in the surface resistance of the transparent conductive layer 1 can be suppressed.
3. Modification examples
In the following modifications, the same members and steps as in the above-described embodiment are denoted by the same reference numerals, and detailed description thereof is omitted. Each modification can exhibit the same operational effects as those of the first embodiment unless specifically described. Further, one embodiment and the modification may be appropriately combined.
In the modification, the transparent conductive layer 1 may be formed of 1 region. The sputtering apparatus includes a single film forming chamber.
In another modification, although not shown, a rare gas having an atomic number larger than that of argon is included in the 1 st region 3 or the 2 nd region 4.
In another modification, the transparent conductive film 5 includes, in order from one side in the thickness direction: a substrate 6, zone 2, zone 4 and zone 1, zone 3.
In another modification, the transparent conductive layer 1 has a repeating structure of the 1 st region 3 and the 2 nd region 4.
In the modification, the functional layer 60 is a plurality of layers, although not shown. The functional layer 60 is disposed on one surface and the other surface of the base sheet 61 in the thickness direction. For example, the functional layer 60 includes an optical adjustment layer and a hard coat layer. The optical adjustment layer is disposed on one surface of the base sheet 61. The hard coat layer is disposed on the other surface of the base sheet 61.
Examples
Hereinafter, examples are shown, and the present invention will be described more specifically. The present invention is not limited to the examples. Specific numerical values such as the blending ratio (content ratio), physical property value, and parameter used in the following description may be substituted for the upper limit (numerical values defined as "below", "insufficient") or the lower limit (numerical values defined as "above", "exceeding") of the blending ratio (content ratio), physical property value, and parameter described in the above-described "specific embodiment" corresponding thereto.
Example 1
< preparation of substrate 6 >
A substrate 6 having a thickness of 52 μm was prepared.
Specifically, a base sheet 61 (thickness 50 μm, manufactured by Toray Industries, inc.) formed of PET was prepared. Next, a hard coat composition (ultraviolet curable resin containing an acrylic resin) is coated on one surface of the base sheet 61 in the thickness direction to form a coating film. Subsequently, the coating film is cured by ultraviolet irradiation. Thus, a hard coat layer 62 having a thickness of 2 μm was formed on one surface of the base sheet 61. Thus, the base material 6 having the base material sheet 61 and the hard coat layer 62 in this order on one side in the thickness direction is produced.
An amorphous transparent conductive layer is formed on one surface of the substrate 6. In the formation of the amorphous transparent conductive layer, the 1 st sputtering step and the 2 nd sputtering step are sequentially performed. The 1 st sputtering process and the 2 nd sputtering process are reactive magnetron sputtering. In the 1 st sputtering step, the amorphous 1 st region 3 is formed on one surface of the base material 6. In the 2 nd sputtering step, the amorphous 2 nd region 4 is formed on one surface of the 1 st region 3.
< 1 st sputtering Process >
As the 1 st target, a sintered body of indium oxide and tin oxide was used. The tin oxide concentration in the sintered body was 10 mass%. A voltage was applied to target 1 using a DC power supply. The horizontal magnetic field strength on the 1 st target was set to 90mT. The film formation temperature was set at-5 ℃. Further, the 1 st film forming chamber was evacuated until the ultimate vacuum in the 1 st film forming chamber was 0.9X10 -4 Pa, thereby degassing the base material 6. Thereafter, kr as a sputtering gas and oxygen as a reactive gas were introduced into the 1 st film forming chamber, and the gas pressure in the 1 st film forming chamber was set to 0.2Pa. The ratio of the amount of oxygen introduced into the 1 st film forming chamber to the total amount of Kr and oxygen introduced was about 2.6% by flow. As shown in fig. 3, the oxygen introduction amount was adjusted so that the resistivity of the amorphous 1 st region 3 became 6.5x10 in the region X of the resistivity-oxygen introduction amount curve -4 Omega cm. The thickness of region 1, 3, was 11nm.
< 2 nd sputtering Process >
As the 2 nd target, a sintered body of indium oxide and tin oxide was used. The tin oxide concentration in the sintered body was 3 mass%. A DC power supply was used to apply a voltage to target 2. The horizontal magnetic field strength on the 2 nd target was set to 90mT. The film formation temperature was set at-5 ℃. Further, the 2 nd film forming chamber was evacuated until the ultimate vacuum in the 2 nd film forming chamber in the DC magnetron sputtering apparatus was 0.9X10 -4 Pa, and thereafter introducing Kr as a sputtering gas and oxygen as a reactive gas into the 2 nd film forming chamber to thereby form a film in the 2 nd film forming chamberThe air pressure was set to 0.2Pa. The ratio of the amount of oxygen introduced into the 2 nd film forming chamber to the total amount of Kr and oxygen introduced was about 2.5% by flow. As shown in fig. 3, the oxygen introduction amount was adjusted so that the resistivity of the amorphous 2 nd region 4 became 6.5x10 in the region X of the resistivity-oxygen introduction amount curve -4 Omega cm. The thickness of region 2, 4, is 11nm.
< crystallization of amorphous transparent conductive layer >
Thereafter, the laminate including the base material 6 and the amorphous transparent conductive layer is heated by contacting the laminate with a heating roller in a vacuum heating apparatus. The heating temperature was 160℃and the heating time was 0.1 hour. Thereby, the amorphous transparent conductive layer is crystallized. Thereby, the crystalline transparent conductive layer 1 is formed. For the thickness of the transparent conductive layer 1, the thickness was 22nm.
Thus, a transparent conductive film 5 having a base material 6 and a crystalline transparent conductive layer 1 in this order on one side in the thickness direction was produced.
Comparative example 1]
In the same manner as in example 1, the 1 st sputtering step and the 2 nd sputtering step were performed to produce the transparent conductive thin film 5. Among them, the following aspects are changed.
< 1 st sputtering Process >
In the 1 st sputtering step, the sputtering gas was changed to argon, the gas pressure in the sputtering film forming apparatus was changed to 0.4Pa, and the ratio of the amount of oxygen introduced into the 1 st film forming chamber to the total amount of argon and oxygen introduced was set to about 1.5% by flow. The 1 st region 3 having a thickness of 19nm was formed by the 1 st sputtering step.
< 2 nd sputtering Process >
In the 2 nd sputtering step, the sputtering gas was changed to argon, the gas pressure in the 2 nd film forming chamber was changed to 0.4Pa, and the ratio of the amount of oxygen introduced into the 1 st film forming chamber to the total amount of argon and oxygen introduced was set to about 1.5% by flow. Through the 2 nd sputtering step, the 2 nd region 4 having a thickness of 3nm was formed. The thickness of the transparent conductive layer 1 was 22nm.
< crystallization of amorphous transparent conductive layer >
The amorphous transparent conductive layer was heated in a hot air oven at 160 ℃ for 0.5 hours. Thereby, the crystalline transparent conductive layer 1 is formed.
< evaluation >
The following items were evaluated for the transparent conductive films 5 of example 1 and comparative example 1.
< thickness >
The thickness of the transparent conductive layer 1 was measured by FE-TEM observation. Specifically, first, a sample for cross-section observation of the transparent conductive layer 1 was prepared by FIB micro-sampling. In the FIB micro-sampling method, an acceleration voltage was set to 10kV using a FIB device (trade name "FB2200", hitachi). Next, the thickness of the transparent conductive layer 1 in the sample for cross-sectional observation was measured by FE-TEM observation. In FE-TEM observation, an acceleration voltage was set at 200kV using an FE-TEM apparatus (trade name "JEM-2800", manufactured by JEOL).
Before forming the 2 nd region 4, a cross-sectional observation sample was prepared from the 1 st region 3, and FE-TEM observation was performed on the sample to calculate the thickness of the 1 st region 3.
The thickness of the 1 st region 3 is subtracted from the thickness of the transparent conductive layer 1, thereby calculating the thickness of the 2 nd region 4.
<(440) Integral intensity I of peak of face 440 Integrated intensity I of peak relative to (222) plane 222 Ratio (I) 440 /I 222 )>
The integrated intensity I of the peak at the (440) plane of the transparent conductive layer 1 was obtained by performing X-ray diffraction measurement using a horizontal X-ray diffraction apparatus (trade name "Smart Lab", manufactured by Rigaku Corporation) based on the following measurement conditions 440 Integrated intensity I of peak relative to (222) plane 222 Ratio (I) 440 /I 222 ). The results are set forth in Table 1.
[ measurement conditions ]
Parallel beam optical configuration
Light source: cukα rays (wavelength:)
and (3) outputting: 45kV and 200mA
Incident side slit system: soxhlet slit 5.0 degrees
Entrance slit: 1.000mm
Light receiving slit: 20.100mm
Light receiving side slit: parallel slit splitter (PSA) 0.114deg.
A detector: multi-dimensional pixel detector Hypix-3000
Sample stage: a sample obtained by bonding glass to the base material 6 of the transparent conductive film 5 via an adhesive layer was left to stand on a sample plate (4-inch wafer sample plate).
Scanning axis: 2 theta/theta (Out of Plane measurement)
Step interval: 0.02 degree
Measuring speed: 0.8 DEG/min
Measurement range: 10-90 DEG
The X-ray peak profile was obtained by subtracting the background derived from the substrate 6 (the substrate 6 heated under the same conditions as the transparent conductive layer 1 of example 1 and comparative example 1). Then, using analysis software (software name "SmartLab StudioII"), the profile of the X-ray diffraction peak corresponding to the (222) plane and the profile of the X-ray diffraction peak corresponding to the (440) plane were prepared so that 2θ was in the range of 49.8 ° to 51.8 °. Fitting of the X-ray diffraction peaks (peak shape: divided PearsonVII function, background type: B-spline, fitting condition: automatic) to each profile was performed to obtain the integral intensity I of the X-ray diffraction peak of the (222) plane (222) (unit: count DEG), and integrated intensity I of the peak of the X-ray diffraction of the (440) plane 440 (unit: count °).
Integrated intensity I of peak diffracted by (440) plane X-ray 440 Dividing the integrated intensity I of the peak of the X-ray diffraction of the (222) plane 222 。
< grain diameter >
The crystal grain diameter of the transparent conductive layer 1 was obtained by observing one surface of the transparent conductive layer 1 with FE-SEM (apparatus: manufactured by Hitachi, SU 8020). Specifically, after the transparent conductive layer 1 was fixed to a stage, surface FE-SEM observation (acceleration voltage: 0.8kV, observation image: secondary electron image) was performed, and the transparent conductive layer 1 was photographed in a plan view. The magnification is adjusted so that the crystal grains can be clearly confirmed.
Then, the captured image is subjected to an image analysis process, whereby the area of the region defined by the grain boundaries (regions within the grain boundaries) is determined from the number of pixels present in the region, and the diameter of a circle having the same area as the area is determined as the crystal grain diameter (circle equivalent diameter).
As a result, the grain diameter of example 1 was 0.6. Mu.m. The grain diameter of comparative example 1 was 0.4. Mu.m.
< test for resistance to heating >
The surface resistance of the transparent conductive layer 1 was measured to obtain an initial surface resistance R0.
Thereafter, the transparent conductive film 5 was put into a hot air oven at 140℃for 1 hour. After the transparent conductive film 5 was taken out of the hot air oven, the surface resistance of the transparent conductive film 5 was obtained as the surface resistance R1 after heating.
The initial surface resistance R0 was divided by the surface resistance R1 after heating, and the rate of increase in surface resistance before and after the heating test was obtained. The results are set forth in Table 1.
The increase rate of the surface resistance before and after the heating test of example 1 was less than 1, which revealed that the increase of the surface resistance after the heating test was suppressed.
In contrast, the increase rate of the surface resistance before and after the heating test of comparative example 1 exceeded 1, and it was found that the surface resistance after the heating test increased.
< confirmation of Kr atom in transparent conductive layer 1>
The transparent conductive layer 1 in example 1 was confirmed to contain Kr atoms as follows.
First, using a scanning fluorescent X-ray analyzer (trade name "ZSX primus iv", manufactured by Rigaku Corporation), fluorescent X-ray analysis measurement was repeated 5 times under the following measurement conditions, and an average value of each scanning angle was calculated to manufacture an X-ray spectrum. Then, it was confirmed that a peak was present near the scanning angle of 28.2 ° in the produced X-ray spectrum, and that Kr atoms were contained in the transparent conductive layer 1. In comparative example 1, no peak was observed.
[ measurement conditions ]
A spectrum; kr-KA
Diameter measurement: 30mm
Atmosphere: vacuum
And (3) target: rh (rhodium)
Tube voltage: 50kV
Tube current: 60mA
1 st order filter: ni40
Scan angle (deg): 27.0 to 29.5
Step size (deg): 0.020
Speed (deg/min): 0.75
An attenuator: 1/1
Slit: s2
A spectroscopic crystal: liF (200)
A detector: SC (SC)
PHA：100～300
< confirmation of Ar in transparent conductive layer 1>
The transparent conductive layer 1 of comparative example 1 was confirmed to contain Ar by Rutherford Backscattering Spectrometry (RBS).
Specifically, in+sn (In and Sn are difficult to be separately measured by rutherford backscattering spectrometry, and thus are evaluated as a total of 2 elements) and O, ar are measured as detection elements, and the presence of Ar In the transparent conductive layer is confirmed. The apparatus and measurement conditions were as follows.
< use device >
Pelletron 3SDH (National Electrostatics Corporation system)
< measurement conditions >
Incident ions: 4He+ +
Incident energy: 2300keV
Incidence angle: 0deg
Scattering angle: 160deg
Sample current: 6nA
Beam diameter:
in-plane rotation: without any means for
Irradiation amount: 75 mu C
TABLE 1
The present invention is provided as an exemplary embodiment of the present invention, but it is merely illustrative and not limitative. Variations of the present invention that are obvious to those skilled in the art are encompassed in the foregoing claims.
Industrial applicability
Transparent conductive layers are used in optical articles.
Description of the reference numerals
1. Transparent conductive layer
2. Rare gas
5. Transparent conductive film
6. Substrate material

Claims (6)

1. A transparent conductive layer, comprising: an inorganic oxide containing a rare gas having an atomic number larger than that of argon,
integrated intensity I of peak of (440) plane when X-ray diffracting the transparent conductive layer 440 Integrated intensity I of peak relative to (222) plane 222 Ratio (I) 440 /I 222 ) Less than 0.130.
2. The transparent conductive layer of claim 1 having a thickness of less than 150nm.
3. The transparent conductive layer according to claim 1 or 2, wherein the inorganic oxide is an indium tin composite oxide.
4. A transparent conductive film is provided with: a substrate comprising a resin, and the transparent conductive layer according to claim 1 or 2.
5. An article provided with the transparent conductive layer according to claim 1 or 2.
6. An article comprising the transparent conductive film according to claim 4.
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JP2005259628A (en) * 2004-03-15 2005-09-22 Konica Minolta Holdings Inc Method for forming transparent conductive film, transparent conductive film formed thereby, and article having the same
CN106062888A (en) * 2014-12-22 2016-10-26 日东电工株式会社 Transparent conductive film

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JP6261987B2 (en) 2013-01-16 2018-01-17 日東電工株式会社 Transparent conductive film and method for producing the same
JP2021018956A (en) * 2019-07-23 2021-02-15 Tdk株式会社 Transparent conductor and organic device
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CN1302442A (en) * 1999-02-24 2001-07-04 帝人株式会社 Transparent conductive laminate, its manufacturing method, and display comprising transparent conductive laminate
JP2005259628A (en) * 2004-03-15 2005-09-22 Konica Minolta Holdings Inc Method for forming transparent conductive film, transparent conductive film formed thereby, and article having the same
CN106062888A (en) * 2014-12-22 2016-10-26 日东电工株式会社 Transparent conductive film

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