CN115298758A

CN115298758A - Transparent conductive film

Info

Publication number: CN115298758A
Application number: CN202180021919.7A
Authority: CN
Inventors: 梶原大辅; 藤野望; 碓井圭太
Original assignee: Nitto Denko Corp
Current assignee: Nitto Denko Corp
Priority date: 2020-03-19
Filing date: 2021-03-18
Publication date: 2022-11-04
Also published as: TW202147343A; JPWO2021187580A1; JP7240513B2; WO2021187580A1; KR20220155286A; JP2022118004A

Abstract

The transparent conductive film (X) of the present invention comprises a transparent substrate (10) and an amorphous light-transmitting conductive layer (20) in this order along the thickness direction (D). The light-transmitting conductive layer (20) contains krypton and has a size of 40 × 10 ¹⁹ cm ^‑3 The above current carryingThe sub-density.

Description

Transparent conductive film

Technical Field

The present invention relates to a transparent conductive film.

Background

Conventionally, a transparent conductive film including a transparent base film and a transparent conductive layer (transparent conductive layer) in this order in a thickness direction is known. The light-transmitting conductive layer is used as a conductor film for patterning a transparent electrode in various devices such as a liquid crystal display, a touch panel, and a photosensor. In the process of forming the light-transmissive conductive layer, an amorphous film of a light-transmissive conductive material is first formed on the base thin film by, for example, a sputtering method (film-forming step). Subsequently, the amorphous light-transmitting conductive layer on the base film is crystallized by heating (crystallization step). In the sputtering method in the film forming step, conventionally, an inert gas such as argon gas is used as a sputtering gas for striking a target (film forming material supplying material) and ejecting atoms on the target surface. A related art of such a transparent conductive film is described in, for example, patent document 1 below.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2017-71850

Disclosure of Invention

Problems to be solved by the invention

From the viewpoint of the production efficiency of the transparent conductive film, it is preferable that the crystallization rate of the transparent conductive layer by heating in the crystallization step is high.

However, when the crystallization rate of the conventional transparent conductive layer by heating is high, the transparent conductive layer is easily crystallized even under a low temperature (e.g., room temperature) condition. When a transparent conductive film including a light-transmitting conductive layer having a high crystallization rate is temporarily stored at room temperature, for example, the light-transmitting conductive layer may be partially crystallized. In the crystallization step of the transparent conductive layer, strain is generated at the boundary between the portion that starts to be crystallized and the portion that has already been crystallized during storage. This strain may cause cracks in the crystalline light-transmitting conductive layer to be formed. It is not preferable that cracks occur in the transparent conductive layer from the viewpoint of the production yield of the transparent conductive thin film and the production yield of a device including the transparent conductive thin film. Therefore, the amorphous light-transmitting conductive layer is required to be able to be stored well while suppressing crystallization when stored under low-temperature (e.g., room temperature) conditions.

The invention provides a transparent conductive film suitable for realizing high crystallization speed of a light-transmitting conductive layer and ensuring good storage property.

Means for solving the problems

The invention [1]Comprises a transparent conductive film comprising a transparent substrate and an amorphous light-transmitting conductive layer containing krypton and having a thickness of 40X 10 ¹⁹ cm ^-3 The above carrier density.

The invention [2] is the transparent conductive thin film according to [1], wherein the light-transmitting conductive layer contains an indium-containing conductive oxide.

The invention [3] is the transparent conductive film according to [1] or [2], wherein the light-transmitting conductive layer has a thickness of 40nm or more.

Invention [4 ]]Comprises the above [1]～[3]The transparent conductive film as described in any one of the above, wherein the light-transmitting conductive layer has a thickness of 18cm ² A Hall mobility of/V.s or less.

The invention [5]Comprises the above [1]～[4]The transparent conductive film according to any one of the above items, wherein the light-transmitting conductive layer has a thickness of 2.2X 10 after heat treatment at 130 ℃ for 1.5 hours ^-4 Resistivity of not more than Ω · cm.

ADVANTAGEOUS EFFECTS OF INVENTION

Hair brushThe transparent conductive layer of the transparent conductive film contains krypton and has a size of 40X 10 ¹⁹ cm ^-3 The carrier density is preferably higher than the above density in order to achieve a high crystallization rate of the transparent conductive layer and to ensure good storage stability.

Drawings

Fig. 1 is a schematic cross-sectional view of one embodiment of the transparent conductive film of the present invention.

Fig. 2 shows a method for manufacturing the transparent conductive film shown in fig. 1. Fig. 2A shows a step of preparing a resin film, fig. 2B shows a step of forming a functional layer on the resin film, and fig. 2C shows a step of forming a light-transmitting conductive layer on the functional layer.

Fig. 3 shows a case where the amorphous light-transmitting conductive layer is converted into a crystalline light-transmitting conductive layer in the transparent conductive film shown in fig. 1.

Fig. 4 shows a case where the light-transmitting conductive layer in the transparent conductive film shown in fig. 1 is patterned.

Fig. 5 is a graph showing a relationship between an amount of oxygen introduced when the transparent conductive layer is formed by the sputtering method and a surface resistance of the formed transparent conductive layer.

Detailed Description

Fig. 1 is a schematic cross-sectional view of a transparent conductive film X as one embodiment of the transparent conductive film of the present invention. The transparent conductive film X includes a transparent substrate 10 and a light-transmitting conductive layer 20 in this order on one surface side in the thickness direction D. The transparent conductive thin film X has a shape spreading in a direction (plane direction) orthogonal to the thickness direction D. The transparent conductive film X is one element included in a touch sensor device, a light control element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shielding member, an illumination device, an image display device, and the like.

In the present embodiment, the transparent substrate 10 includes the resin film 11 and the functional layer 12 in this order on one surface side in the thickness direction D. The transparent substrate 10 has a shape extending in a direction (plane direction) orthogonal to the thickness direction D.

The resin film 11 is a flexible transparent resin film. Examples of the material of the resin film 11 include polyester resins, polyolefin resins, acrylic resins, polycarbonate resins, polyethersulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, and polystyrene resins. As the polyester resin, for example, polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate are cited. As the polyolefin resin, for example, polyethylene, polypropylene, and cycloolefin polymer (COP) can be cited. Examples of the acrylic resin include polymethacrylates. As a material of the resin film 11, a polyolefin resin is preferably used, and COP is more preferably used, from the viewpoint of, for example, transparency and strength.

The surface of the resin film 11 on the functional layer 12 side may be subjected to a surface modification treatment. As the surface modification treatment, for example, corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment can be cited.

The thickness of the resin film 11 is preferably 1 μm or more, more preferably 10 μm or more, and further preferably 30 μm or more. The thickness of the resin film 11 is preferably 300 μm or less, more preferably 200 μm or less, further preferably 100 μm or less, and particularly preferably 75 μm or less. These configurations relating to the thickness of the resin film 11 are suitable for ensuring the handleability of the transparent conductive film X.

The total light transmittance (JIS K7375-2008) of the resin film 11 is preferably 60% or more, more preferably 80% or more, and further preferably 85% or more. Such a configuration is suitable for ensuring transparency required for the transparent conductive film X when the transparent conductive film X is provided in a touch sensor device, a light control element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shielding member, an illumination device, an image display device, or the like. The total light transmittance of the resin film 11 is, for example, 100% or less.

In the present embodiment, the functional layer 12 is located on one surface of the resin film 11 in the thickness direction D. In the present embodiment, the functional layer 12 is a hard coat layer for making it difficult to scratch the exposed surface (upper surface in fig. 1) of the light-transmissive conductive layer 20.

The hard coat layer is a cured product of the curable resin composition. Examples of the resin contained in the curable resin composition include polyester resins, acrylic resins, urethane resins, amide resins, silicone resins, epoxy resins, and melamine resins. Examples of the curable resin composition include an ultraviolet curable resin composition and a thermosetting resin composition. Since curing can be performed without heating at a high temperature, it is preferable to use an ultraviolet-curable resin composition as the curable resin composition from the viewpoint of contributing to an improvement in the production efficiency of the transparent conductive film X. Specific examples of the ultraviolet-curable resin composition include a composition for forming a hard coat layer described in japanese patent application laid-open No. 2016-179686.

The surface of the functional layer 12 on the side of the light-transmissive conductive layer 20 may be subjected to a surface modification treatment. As the surface modification treatment, for example, corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment can be cited.

The thickness of the functional layer 12 as the hard coat layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, and further preferably 1 μm or more. Such a configuration is suitable for allowing the light-transmissive conductive layer 20 to exhibit sufficient scratch resistance. From the viewpoint of ensuring the transparency of the functional layer 12, the thickness of the functional layer 12 as a hard coat layer is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less.

The thickness of the transparent substrate 10 is preferably 1 μm or more, more preferably 10 μm or more, further preferably 15 μm or more, and particularly preferably 30 μm or more. The thickness of the transparent substrate 10 is preferably 310 μm or less, more preferably 210 μm or less, further preferably 110 μm or less, and particularly preferably 80 μm or less. These configurations relating to the thickness of the transparent substrate 10 are suitable for ensuring the handleability of the transparent conductive thin film X.

The total light transmittance (JIS K7375-2008) of the transparent substrate 10 is preferably 60% or more, more preferably 80% or more, and further preferably 85% or more. Such a configuration is suitable for ensuring transparency required for the transparent conductive film X when the transparent conductive film X is provided in a touch sensor device, a light control element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shielding member, an illumination device, an image display device, or the like. The total light transmittance of the transparent substrate 10 is, for example, 100% or less.

In the present embodiment, the light-transmissive conductive layer 20 is located on one surface of the transparent substrate 10 in the thickness direction D. The light-transmitting conductive layer 20 is an amorphous film having both light-transmitting property and electrical conductivity. The amorphous transparent conductive layer 20 is converted into a crystalline transparent conductive layer (the transparent conductive layer 20' described later) by heating, and the resistivity is reduced.

The light-transmitting conductive layer 20 is a layer formed of a light-transmitting conductive material. The translucent conductive material contains, for example, a conductive oxide as a main component.

Examples of the conductive oxide include metal oxides containing at least one metal or semimetal selected from the group consisting of In, sn, zn, ga, sb, ti, si, zr, mg, al, au, ag, cu, pd, and W. Specifically, as the conductive oxide, an indium-containing conductive oxide and an antimony-containing conductive oxide can be cited. Examples of the conductive oxide containing indium include indium tin composite oxide (ITO), indium zinc composite oxide (IZO), indium gallium composite oxide (IGO), and indium gallium zinc composite oxide (IGZO). The antimony-containing conductive oxide includes, for example, antimony tin composite oxide (ATO). From the viewpoint of achieving high transparency and good conductivity, as the conductive oxide, indium-containing conductive oxide is preferably used, and ITO is more preferably used. The ITO contains a metal or a semimetal other than In and Sn In an amount less than the respective contents of In and Sn.

When ITO is used as the conductive oxide, the content of tin oxide In the transparent conductive layer 20 is relative to indium oxide (In) ₂ O ₃ ) With tin oxide (SnO) ₂ ) The ratio of the total content (tin oxide content) of (a) is preferably 1 mass% or moreMore preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 7% by mass or more. Such a configuration is suitable for ensuring the durability of the light-transmissive conductive layer 20. In addition, from the viewpoint of obtaining the light-transmitting conductive layer 20 that is easily crystallized by heating, the content ratio of tin oxide is preferably 15% by mass or less, more preferably 13% by mass or less, and still more preferably 12% by mass or less. The content ratio of tin oxide is determined from an XPS spectrum obtained by measuring an object to be measured by X-ray Photoelectron Spectroscopy (X-ray Photoelectron Spectroscopy).

The content ratio of tin oxide in the light-transmitting conductive layer 20 may be different in the thickness direction D. For example, the light-transmitting conductive layer 20 may include a first layer having a relatively high tin oxide content and a second layer having a relatively low tin oxide content in this order from the transparent substrate 10 side. The tin oxide content in the first layer is preferably 5 mass% or more, and more preferably 8 mass% or more. The tin oxide content in the first layer is preferably 15 mass% or less, and more preferably 13 mass% or less. The content of tin oxide in the second layer is preferably 0.5% by mass or more, and more preferably 2% by mass or more. The content ratio of tin oxide in the second layer is preferably 8% by mass or less, and more preferably 5% by mass or less. The thickness ratio of the first layer in the thickness of the light-transmitting conductive layer 20 is preferably 50% or more, more preferably 60% or more, and further preferably 70% or more. The thickness ratio of the second layer in the thickness of the light-transmitting conductive layer 20 is preferably 50% or less, more preferably 40% or less, and still more preferably 30% or less.

The light-transmitting conductive layer 20 contains krypton (Kr) as a rare gas atom. In the present embodiment, the rare gas atoms in the transparent conductive layer 20 are derived from rare gas atoms used as a sputtering gas in a sputtering method described later. In the present embodiment, the light-transmitting conductive layer 20 is a film (sputtered film) formed by a sputtering method.

The transparent conductive layer 20, which is a sputtered film formed using Kr as a sputtering gas, is suitable for achieving a high crystallization rate of the transparent conductive layer, compared to a conventional transparent conductive layer, which is a sputtered film formed using Ar as a sputtering gas. That is, the configuration in which the light-transmitting conductive layer 20 contains Kr is suitable for achieving a high crystallization rate of the light-transmitting conductive layer 20. This configuration is suitable for suppressing crystallization of the amorphous light-transmitting conductive layer 20 at a low temperature (e.g., room temperature), and is therefore suitable for ensuring good storage stability. Whether or not Kr is present in the light-transmitting conductive layer 20 is determined by, for example, fluorescent X-ray analysis as described later with respect to the examples.

The content ratio of Kr in the light-transmitting conductive layer 20 is, for example, 0.5 atomic% or less, preferably 0.3 atomic% or less, and more preferably 0.2 atomic% or less, in the entire region in the thickness direction D. This structure is suitable for achieving good crystal growth and formation of large crystal grains when the amorphous transparent conductive layer 20 is crystallized by heating, and therefore is suitable for obtaining a low resistance of the transparent conductive layer 20' (the larger the crystal grains in the transparent conductive layer 20', the lower the resistance of the transparent conductive layer 20 '). The content of Kr in the transparent conductive layer 20 is, for example, 0.0001 atomic% or more in the entire region in the thickness direction D.

The content ratio of Kr in the light-transmitting conductive layer 20 may be different in the thickness direction D. For example, the content ratio of Kr may be increased or decreased as it goes away from the transparent substrate 10 in the thickness direction D. Alternatively, a partial region in which the content ratio of Kr increases with distance from the transparent substrate 10 in the thickness direction D may be located on the transparent substrate 10 side, and a partial region in which the content ratio of Kr decreases with distance from the transparent substrate 10 may be located on the opposite side of the transparent substrate 10. Alternatively, a partial region in which the content ratio of Kr decreases with distance from the transparent substrate 10 in the thickness direction D may be located on the transparent substrate 10 side, and a partial region in which the content ratio of Kr increases with distance from the transparent substrate 10 may be located on the opposite side of the transparent substrate 10.

The light-transmitting conductive layer 20 preferably contains only Kr as a rare gas atom. Such a configuration is preferable in view of achieving low resistance of the light-transmitting conductive layer 20'. This configuration is suitable for suppressing crystallization of the amorphous light-transmitting conductive layer 20 at low temperature, and is therefore suitable for ensuring good storage stability.

When the light-transmitting conductive layer 20 contains a rare gas atom other than Kr, examples of the rare gas atom other than Kr include argon (Ar) and xenon (Xe). From the viewpoint of reducing the production cost of the transparent conductive thin film X, the light-transmissive conductive layer 20 preferably does not contain Xe.

The content of rare gas atoms (including Kr) in the transparent conductive layer 20 is, for example, 0.5 atomic% or less, preferably 0.3 atomic% or less, and more preferably 0.2 atomic% or less, in the entire region in the thickness direction D. This structure is suitable for achieving good crystal growth and formation of large crystal grains when the amorphous transparent conductive layer 20 is crystallized by heating, and is therefore suitable for obtaining a low-resistance transparent conductive layer 20'. The content ratio of the rare gas atoms in the transparent conductive layer 20 is, for example, 0.0001 atomic% or more in the entire region in the thickness direction D.

The thickness of the light-transmitting conductive layer 20 is, for example, 10nm or more, preferably 30nm or more, more preferably 35nm or more, and still more preferably 40nm or more. Such a configuration is suitable for reducing the resistance of the transparent conductive layer 20'. This configuration is suitable for suppressing crystallization of the amorphous light-transmitting conductive layer 20 at low temperature, and is therefore suitable for ensuring good storage stability.

The thickness of the light-transmitting conductive layer 20 is, for example, 1000nm or less, preferably less than 300nm, more preferably 250nm or less, further preferably 200nm or less, further preferably 160nm or less, particularly preferably less than 150nm, and most preferably 148nm or less. This configuration is suitable for reducing the compressive residual stress of the transparent conductive layer 20 and suppressing the warpage of the transparent conductive film X.

The total light transmittance (JIS K7375-2008) of the light-transmitting conductive layer 20 is preferably 60% or more, more preferably 80% or more, and further preferably 85% or more. Such a configuration is suitable for ensuring transparency of the light-transmitting conductive layer 20. The total light transmittance of the light-transmitting conductive layer 20 is, for example, 100% or less.

The surface resistance of the transparent conductive layer 20 is preferably 200 Ω/\9633orless, more preferably 175 Ω/\9633orless. This structure is suitable for forming the low-resistance light-transmitting conductive layer 20' from the light-transmitting conductive layer 20. The surface resistance of the transparent conductive layer 20 is, for example, 120 Ω/\9633ormore. The surface resistance of the conductive film can be measured by a four-terminal method according to JIS K7194.

The electrical resistivity of the light-transmitting conductive layer 20 after heat treatment at 130 ℃ for 1.5 hours is preferably 2.2 × 10 ^-4 Omega cm or less, more preferably 2X 10 ^-4 Omega cm or less, more preferably 1.9X 10 ^-4 Omega cm or less, particularly preferably 1.8X 10 ^-4 Omega cm or less. This structure is suitable for forming the low-resistance light-transmitting conductive layer 20' from the light-transmitting conductive layer 20. The transparent conductive layer 20 has a resistivity of, for example, 7.5 × 10 ^-4 Omega cm or more. The resistivity is determined by multiplying the surface resistance by the thickness.

The carrier density of the transparent conductive layer 20 was 40 × 10 ¹⁹ cm ^-3 Above, preferably 45 × 10 ¹⁹ cm ^-3 Above, more preferably 47 × 10 ¹⁹ cm ^-3 The above. The carrier density of the light-transmitting conductive layer 20 is preferably 100 × 10 ¹⁹ cm ^-3 Hereinafter, more preferably 80X 10 ¹⁹ cm ^-3 The following. Such a configuration is suitable for achieving a high crystallization rate of the transparent conductive layer 20. In addition, this configuration is suitable for suppressing crystallization of the amorphous light-transmitting conductive layer 20 under low temperature conditions, and is therefore suitable for ensuring good storage stability. The carrier density can be adjusted by, for example, adjusting the content ratio of Kr in the transparent conductive layer 20 and adjusting various conditions when the transparent conductive layer 20 is formed by sputtering. Examples of such conditions include the temperature of the film formation base (transparent substrate 10 in the present embodiment) of the light-transmitting conductive layer 20 and the amount of oxygen introduced into the film formation chamber. The resistivity can be adjusted by adjusting the surface properties of the film formation base of the light-transmitting conductive layer 20 (in the present embodiment, the functional layer 12)Surface properties).

The Hall mobility of the light-transmitting conductive layer 20 is preferably 5cm ² More preferably 8cm or more ² More preferably 10cm or more ² More than V.s. The Hall mobility of the light-transmitting conductive layer 20 is preferably 18cm ² V.s or less, more preferably 17cm ² Has a value of/V.s or less. Such a configuration is suitable for achieving a high crystallization rate of the transparent conductive layer 20. This configuration is suitable for suppressing crystallization of the amorphous light-transmitting conductive layer 20 at low temperature, and is therefore suitable for ensuring good storage stability. The hall mobility can be adjusted by, for example, adjusting the content ratio of Kr in the light-transmissive conductive layer 20 and adjusting various conditions when the light-transmissive conductive layer 20 is formed by sputtering. Examples of such conditions include the temperature of the film formation base (transparent substrate 10 in the present embodiment) of the amorphous light-transmissive conductive layer, the sputtering power on the substrate side (transparent substrate 10 side in the present embodiment), and the like. The hall mobility can also be adjusted by adjusting the surface properties (in the present embodiment, the surface properties of the functional layer 12) such as the surface shape of the film formation base of the amorphous light-transmitting conductive layer.

The light-transmitting conductive layer is crystalline, for example, as follows. First, the light-transmitting conductive layer (in the transparent conductive film X, the light-transmitting conductive layer 20 on the transparent substrate 10) was immersed in hydrochloric acid having a concentration of 5 mass% at 35 ℃ for 15 minutes. Next, the light-transmitting conductive layer was washed with water and dried. Next, the resistance (inter-terminal resistance) between a pair of terminals spaced apart by 15mm was measured on the exposed plane of the transparent conductive layer (the surface of the transparent conductive film X on the side opposite to the transparent substrate 10 of the transparent conductive layer 20). In this measurement, when the inter-terminal resistance is 10k Ω or less, the transparent conductive layer is crystalline.

The transparent conductive film X is produced, for example, as follows.

First, as shown in fig. 2A, a resin film 11 is prepared.

Next, as shown in fig. 2B, the functional layer 12 is formed on one surface of the resin film 11 in the thickness direction D. The functional layer 12 is formed on the resin film 11, thereby producing the transparent substrate 10.

The functional layer 12 as a hard coat layer can be formed by applying a curable resin composition to the resin film 11 to form a coating film and then curing the coating film. When the curable resin composition contains an ultraviolet curable resin, the coating film is cured by ultraviolet irradiation. When the curable resin composition contains a thermosetting resin, the coating film is cured by heating.

The exposed surface of the functional layer 12 formed on the resin film 11 is subjected to surface modification treatment as necessary. When the plasma treatment is performed as the surface modification treatment, for example, argon gas is used as the inert gas. The discharge power in the plasma processing is, for example, 100W or more, and 500W or less.

Next, as shown in fig. 2C, the light-transmitting conductive layer 20 is formed on the transparent substrate 10 (film formation step). Specifically, a material is deposited on the functional layer 12 of the transparent substrate 10 by a sputtering method, thereby forming the amorphous light-transmissive conductive layer 20.

In the sputtering method, a sputtering film forming apparatus capable of performing a film forming process by a roll-to-roll method is preferably used. In the production of the transparent conductive film X, when a roll-to-roll sputtering film forming apparatus is used, the long transparent base material 10 is advanced from a take-out roll provided in the apparatus to a take-up roll, and a material is formed on the transparent base material 10 to form the transparent conductive layer 20. In this sputtering method, a sputtering film forming apparatus having one film forming chamber may be used, or a sputtering film forming apparatus having a plurality of film forming chambers arranged in sequence along the traveling path of the transparent substrate 10 may be used (in the case of forming the transparent conductive layer 20 including the first layer and the second layer, a sputtering film forming apparatus having a plurality of film forming chambers of 2 or more is used).

In the sputtering method, specifically, a sputtering gas (inert gas) is introduced into a film formation chamber under vacuum conditions, and a negative voltage is applied to a target disposed on a cathode in the film formation chamber. This generates glow discharge to ionize gas atoms, causing the gas ions to strike the target surface at high speed, ejecting target material from the target surface, and depositing the ejected target material on the functional layer 12 in the transparent substrate 10.

As a material of the target disposed on the cathode in the film formation chamber, the conductive oxide described above with respect to the light-transmissive conductive layer 20 is used, and preferably, an indium-containing conductive oxide is used, and more preferably, ITO is used. When ITO is used, the ratio of the content of tin oxide in the ITO to the total content of tin oxide and indium oxide is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, particularly preferably 7% by mass or more, and further preferably 15% by mass or less, more preferably 13% by mass or less, further preferably 12% by mass or less.

The sputtering method is preferably a reactive sputtering method. In the reactive sputtering method, a reactive gas is introduced into the film forming chamber in addition to a sputtering gas.

When the transparent conductive layer 20 containing Kr is formed over the entire region in the thickness direction D, the gas introduced into the film forming chamber contains Kr as a sputtering gas and oxygen as a reactive gas. The sputtering gas may contain an inactive gas other than Kr. Examples of the inert gas other than Kr include rare gas atoms other than Kr. As the rare gas atom, for example, ar and Xe can be cited. When the sputtering gas contains an inert gas other than Kr, the content ratio thereof is preferably 5 vol% or less, and more preferably 3 vol% or less.

In the reactive sputtering method, the ratio of the amount of oxygen introduced into the film forming chamber to the total amount of the sputtering gas and oxygen introduced into the film forming chamber is, for example, 0.1% by flow or more, and is, for example, 5% by flow or less.

The gas pressure in the film forming chamber in film formation by the sputtering method (sputter film formation) is, for example, 0.02Pa or more and, for example, 1Pa or less.

The temperature of the transparent substrate 10 during sputter deposition is, for example, 100 ℃ or lower, preferably 50 ℃ or lower, more preferably 30 ℃ or lower, and is, for example, -20 ℃ or higher, preferably-10 ℃ or higher, more preferably-7 ℃ or higher.

Examples of the power source for applying a voltage to the target include a DC power source, an AC power source, an MF power source, and an RF power source. As the power source, a DC power source and an RF power source may be used in combination. The discharge voltage during sputter deposition is, for example, 200V or more and, for example, 400V or less.

For example, the transparent conductive thin film X can be manufactured by the above-described operation.

As schematically shown in fig. 3, the light-transmissive conductive layer 20 in the transparent conductive thin film X may be patterned. The light-transmitting conductive layer 20 can be patterned by etching the light-transmitting conductive layer 20 through a predetermined etching mask. The patterned transparent conductive layer 20 functions as a wiring pattern, for example.

In addition, the transparent conductive layer 20 in the transparent conductive thin film X is converted into a crystalline transparent conductive layer 20' (shown in fig. 4) by heating. Examples of the heating means include an infrared heater and an oven. The heating temperature is, for example, 100 ℃ or higher, preferably 120 ℃ or higher, from the viewpoint of ensuring a high crystallization rate. From the viewpoint of suppressing the influence of heating on the transparent base material 10, the heating temperature is preferably 200 ℃ or lower, more preferably 180 ℃ or lower, and still more preferably 170 ℃ or lower. The heating temperature is preferably 120 ℃ or higher, more preferably 130 ℃ or higher. The heating time is preferably 120 minutes or less, more preferably 90 minutes or less, and further preferably 70 minutes or less. The heating time is preferably 10 minutes or more, more preferably 20 minutes or more. The patterning of the light-transmissive conductive layer 20 may be performed before or after the heating for crystallization.

The surface resistance of the light-transmitting conductive layer 20' is, for example, 200 Ω/\9633, preferably 100 Ω/\9633, more preferably 50 Ω/\9633, and still more preferably 45 Ω/\9633. The surface resistance of the light-transmitting conductive layer 20' is, for example, 1. Omega./\9633; or more. These configurations relating to the surface resistance are suitable for ensuring low resistance required for the transparent conductive layer 20 'when the transparent conductive film X having the transparent conductive layer 20' is provided in a touch sensor device, a light control element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shielding member, an illumination device, an image display device, or the like.

The resistivity of the light-transmitting conductive layer 20' is preferably 2.2 × 10 ^-4 Omega cm or less, more preferably 2X 10 ^-4 Omega cm or less, more preferably 1.9X 10 ^-4 Omega cm or less, particularly preferably 1.8X 10 ^-4 Omega cm or less. The transparent conductive layer 20' has a resistivity of, for example, 0.1X 10 ^-4 Omega cm or more. These configurations relating to the resistivity are suitable for ensuring low resistance required for the transparent conductive layer 20 'when the transparent conductive film X having the transparent conductive layer 20' is provided in a touch sensor device, a light control element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shielding member, an illumination device, an image display device, or the like.

The total light transmittance (JIS K7375-2008) of the light-transmitting conductive layer 20' is preferably 60% or more, more preferably 80% or more, and further preferably 85% or more. Such a configuration is suitable for ensuring transparency of the light-transmitting conductive layer 20'. The total light transmittance of the light-transmitting conductive layer 20' is, for example, 100% or less.

In the transparent conductive film X, as described above, the light-transmitting conductive layer 20 contains krypton, and the carrier density of the light-transmitting conductive layer 20 is 40 × 10 ¹⁹ cm ^-3 Above, preferably 45 × 10 ¹⁹ cm ^-3 Above, more preferably 47 × 10 ¹⁹ cm ^-3 The above.

Such a configuration in the transparent conductive film X is suitable for achieving a high crystallization rate of the transparent conductive layer 20 and ensuring good storage stability. Specifically, the examples and comparative examples are shown below.

In the transparent conductive film X, the functional layer 12 may be an adhesion improving layer for achieving high adhesion of the light-transmissive conductive layer (the light-transmissive conductive layer 20 or the light-transmissive conductive layer 20', the same applies hereinafter) to the transparent base 10. The functional layer 12 is preferably configured to be an adhesion-improving layer for ensuring adhesion between the transparent substrate 10 and the light-transmissive conductive layer.

The functional layer 12 may be an index-matching layer (index-matching layer) for matching the reflectance of the surface (one surface in the thickness direction D) of the transparent substrate 10. The configuration in which the functional layer 12 is a refractive index adjustment layer is suitable for a case where the pattern shape of the light-transmitting conductive layer is not easily observed when the light-transmitting conductive layer on the transparent base material 10 is patterned.

The functional layer 12 may be a peeling functional layer for practically peeling the light-transmissive conductive layer from the transparent substrate 10. The functional layer 12 is preferably a release functional layer in a configuration in which the light-transmissive conductive layer is peeled off from the transparent substrate 10 and the light-transmissive conductive layer is transferred to another member.

The functional layer 12 may be a composite layer in which a plurality of layers are connected in the thickness direction D. The composite layer preferably includes 2 or more layers selected from the group consisting of a hard coat layer, an adhesion improving layer, a refractive index adjusting layer, and a release functional layer. Such a constitution is suitable for causing the functional layer 12 to compositely exhibit the above-described functions of the selected layers. In a preferred embodiment, the functional layer 12 includes an adhesion improving layer, a hard coat layer, and a refractive index adjusting layer in this order on one surface side in the thickness direction D of the resin film 11. In another preferred embodiment, the functional layer 12 includes a release functional layer, a hard coat layer, and a refractive index adjustment layer in this order on one surface side in the thickness direction D of the resin film 11.

The transparent conductive film X is used in a state of being bonded to an article and patterned as necessary. The transparent conductive film X is bonded to an article via, for example, a fixing functional layer.

Examples of the article include elements, members, and devices. That is, examples of the article having a transparent conductive film include an element having a transparent conductive film, a member having a transparent conductive film, and a device having a transparent conductive film.

Examples of the element include a light modulating element and a photoelectric conversion element. Examples of the light control element include a current-driven light control element and an electric field-driven light control element. As the current-driven type dimming element, for example, an Electrochromic (EC) dimming element is cited. Examples of the electric field driven type dimming element include a PDLC (polymer discrete liquid crystal) dimming element, a PNLC (polymer network liquid crystal) dimming element, and an SPD (suspended particle device) dimming element. Examples of the photoelectric conversion element include a solar cell. Examples of the solar cell include an organic thin film solar cell and a dye-sensitized solar cell. Examples of the member include an electromagnetic wave shielding member, a heat ray control member, a heater member, and an antenna member. Examples of the device include a touch sensor device, an illumination device, and an image display device.

Examples of the fixing function layer include an adhesive layer and an adhesive layer. The material for the fixing functional layer is not particularly limited as long as it is a material having transparency and exhibiting a fixing function. The fixing functional layer is preferably formed of a resin. Examples of the resin include acrylic resins, silicone resins, polyester resins, polyurethane resins, polyamide resins, polyvinyl ether resins, vinyl acetate/vinyl chloride copolymers, modified polyolefin resins, epoxy resins, fluorine resins, natural rubbers, and synthetic rubbers. The resin is preferably an acrylic resin because it exhibits adhesive properties such as cohesive property, adhesive property, and appropriate wettability, is excellent in transparency, and is excellent in weather resistance and heat resistance.

In order to suppress corrosion of the light transmissive conductive layer 20', a corrosion inhibitor may be blended into the fixing functional layer (resin forming the fixing functional layer). In order to suppress migration of the light-transmissive conductive layer 20', an anti-migration agent (e.g., a material disclosed in japanese patent laid-open No. 2015-022397) may be blended into the fixed functional layer (resin forming the fixed functional layer). In addition, in order to suppress deterioration of the article when used outdoors, an ultraviolet absorber may be blended into the fixing functional layer (resin forming the fixing functional layer). Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxanilide compounds, cyanoacrylate compounds, and triazine compounds.

When the transparent substrate 10 of the transparent conductive film X is fixed to an article via the fixing functional layer, the light-transmissive conductive layer 20 '(including the patterned light-transmissive conductive layer 20') is exposed in the transparent conductive film X. In this case, a cover layer may be disposed on the exposed surface of the transparent conductive layer 20'. The cover layer is a layer covering the transparent conductive layer 20', and can improve the reliability of the transparent conductive layer 20' and suppress functional degradation due to damage to the transparent conductive layer 20'. Such a covering layer is preferably formed of a dielectric material, more preferably a composite material of a resin and an inorganic material. Examples of the resin include the resins described above for the fixing functional layer. As the inorganic material, for example, inorganic oxides and fluorides can be cited. Examples of the inorganic oxide include silicon oxide, titanium oxide, niobium oxide, aluminum oxide, zirconium dioxide, and calcium oxide. Examples of the fluoride include magnesium fluoride. In addition, the above-described preservative, anti-migration agent, and ultraviolet absorber may be blended into the cover layer (mixture of resin and inorganic material).

Examples

The present invention will be specifically explained below with reference to examples. The invention is not limited to the embodiments. Specific numerical values of the amount (content) of blending, physical property values, parameters, and the like described below may be replaced with upper limits (numerical values defined as "below" or "less than") or lower limits (numerical values defined as "above" or "more than") of the amount (content) of blending, physical property values, parameters, and the like described in the above "specific embodiment" in correspondence with them.

[ example 1]

An ultraviolet-curable resin composition containing an acrylic resin was applied to one surface of a long cycloolefin polymer (COP) film (trade name "ZEONOR", 40 μm thick, manufactured by ZEON corporation) as a transparent resin film (substrate) to form a coating film. Subsequently, the coating film was cured by ultraviolet irradiation to form a hard coat layer (thickness: 1 μm). Next, an ultraviolet-curable resin composition (composite resin composition containing zirconia particles) for forming a refractive index adjustment layer was applied on the hard coat layer to form a coating film. Subsequently, the coating film was cured by ultraviolet irradiation, and a refractive index adjustment layer (thickness 90nm, refractive index 1.62) was formed on the hard coat layer. In this manner, a transparent substrate including the resin film, the hard coat layer, and the refractive index adjustment layer in this order is produced (transparent substrate production step).

Next, an amorphous light-transmitting conductive layer having a thickness of 43nm was formed on the hard coat layer in the transparent substrate by a reactive sputtering method (film formation step). In the reactive sputtering method, a sputtering film forming apparatus (DC magnetron sputtering apparatus) capable of performing a film forming process by a roll-to-roll method is used. The conditions for sputter film formation in this example are as follows.

As the target, a sintered body of indium oxide and tin oxide (tin oxide concentration of 10 mass%) was used. As a power source for applying a voltage to the target, a DC power source is used. The horizontal magnetic field strength on the target is set to 90mT. The film formation temperature (temperature of the transparent substrate on which the light-transmitting conductive layer is to be laminated) was set to 20 ℃. Further, the inside of the film forming chamber was evacuated until the degree of vacuum reached in the film forming chamber of the apparatus became 0.8X 10 ^-4 After Pa, kr as a sputtering gas and oxygen as a reactive gas were introduced into the film forming chamber, and the gas pressure in the film forming chamber was set to 0.2Pa. The ratio of the amount of oxygen introduced into the film formation chamber to the total amount of Kr and oxygen introduced into the film formation chamber was about 2% by flow rate, and the amount of oxygen introduced was adjusted so that the oxygen introduction amount was within the region R of the surface resistance-oxygen introduction amount curve and the surface resistance of the formed film became 175. Omega./\963350as shown in FIG. 5. The surface resistance-oxygen incorporation curve shown in fig. 5 can be prepared by examining the dependence of the oxygen incorporation on the surface resistance of the light-transmitting conductive layer when the light-transmitting conductive layer is formed by the reactive sputtering method under the same conditions as described above except for the oxygen incorporation.

The transparent conductive film of example 1 was produced in the same manner as described above. The light-transmitting conductive layer (thickness 43nm, amorphous) of the transparent conductive film of example 1 was formed of a single ITO layer containing Kr.

[ example 2 and comparative example 1]

The transparent conductive films of example 2 and comparative example 1 were produced in the same manner as the transparent conductive film of example 1, except for the following matters.

In the process for producing the transparent conductive thin film of example 2, the amount of oxygen introduced was adjusted so that the surface resistance of the formed film became 135 Ω/\9633inthe film formation step, and the thickness of the formed transparent conductive layer was 55nm.

In the process for producing the transparent conductive thin film of comparative example 1, the thickness of the formed transparent conductive layer was 51nm in the film formation step.

The light-transmitting conductive layer (amorphous) of each of the transparent conductive films of example 2 and comparative example 1 was formed of a single Kr-containing ITO layer.

[ example 3]

The transparent conductive film of example 3 was produced in the same manner as the transparent conductive film of example 1, except that the thickness of the formed transparent conductive layer was set to 41nm (example 2) instead of 43nm in the film formation step. The light-transmitting conductive layer (amorphous) of the transparent conductive film of example 3 was formed of a single ITO layer containing Kr.

[ comparative examples 2 to 4 ]

Transparent conductive films of comparative examples 2 to 4 were produced in the same manner as the transparent conductive film of example 1, except for the following points.

In the process for producing the transparent conductive film of comparative example 2, a long polyethylene terephthalate (PET) film (thickness 50 μm, manufactured by mitsubishi chemical corporation) was used in place of the COP film in the transparent substrate production step, and in the film formation step, ar was used as a sputtering gas, the film formation pressure was set to 0.4Pa, the surface resistance of the formed film was set to 115 Ω/\9633; (comparative example 2), and the oxygen introduction amount was adjusted so that the thickness of the formed light-transmitting conductive layer was set to 35nm.

In the process for producing the transparent conductive thin film of comparative example 3, ar was used as a sputtering gas in the film formation step, and the film formation pressure was set to 0.4Pa, and the surface resistance of the formed film was set to 67. Omega./\9633inthe film formation step, and the oxygen introduction amount was adjusted so that the thickness of the formed transparent conductive layer was set to 70nm (comparative example 2).

In the process for producing the transparent conductive film of comparative example 4, instead of the COP film, a long PET film (thickness 50 μm, manufactured by mitsubishi chemical corporation) was used in the transparent substrate production step, and in the film formation step, ar was used as a sputtering gas, and the amount of oxygen introduced was adjusted so that the surface resistance of the formed film became 64 Ω/\9633 (comparative example 2) and the thickness of the formed transparent conductive layer became 60nm, with the film formation pressure being 0.4Pa.

The light-transmitting conductive layer (crystalline) of each of the transparent conductive thin films of comparative examples 2 to 4 was formed of a single ITO layer containing Ar.

[ comparative example 5 ]

A transparent conductive film of comparative example 5 was produced in the same manner as the transparent conductive film of example 1, except for the following points.

In the film formation step, a first sputter film formation for forming a first layer (thickness: 17 nm) on a transparent substrate and a second sputter film formation for forming a second layer (thickness: 8 nm) on the first layer are sequentially performed.

The conditions for the first sputtering film formation are as follows. As the target, a sintered body of indium oxide and tin oxide (tin oxide concentration of 10 mass%) was used. As a power source for applying a voltage to the target, a DC power source is used. The horizontal magnetic field strength on the target was set to 90mT. The film formation temperature was set at-5 ℃. Further, the inside of the first film forming chamber was evacuated until the degree of vacuum reached in the first film forming chamber of the apparatus became 0.8X 10 ^-4 After Pa, ar as a sputtering gas and oxygen as a reactive gas were introduced into the first film forming chamber, and the pressure in the film forming chamber was set to 0.4Pa. The amount of oxygen introduced into the film forming chamber was adjusted so that the surface resistance of the formed film became 230. Omega./\9633j.

The conditions for the second sputtering film formation are as follows. As the target, a sintered body of indium oxide and tin oxide (tin oxide concentration of 3 mass) was used%). The second film forming chamber was evacuated until the degree of vacuum in the second film forming chamber of the apparatus reached 0.8X 10 ^-4 After Pa, ar as a sputtering gas and oxygen as a reactive gas were introduced into the second film formation chamber, and the pressure in the film formation chamber was set to 0.4Pa. Other conditions of the second sputtering film formation are the same as those of the first sputtering film formation.

The light-transmitting conductive layer (thickness 25nm, amorphous) of the transparent conductive film of comparative example 5 had a first layer (thickness 17 nm) formed of an Ar-containing ITO layer and a second layer (thickness 8 nm) formed of an Ar-containing ITO layer in this order from the transparent base material side.

Thickness of light-transmitting conductive layer

The thicknesses of the light-transmitting conductive layers in the transparent conductive films of examples 1 to 3 and comparative examples 1 to 5 were measured by FE-TEM observation. Specifically, first, samples for observing the cross section of each of the transparent conductive layers in examples 1 to 3 and comparative examples 1 to 5 were prepared by the FIB microsampling method. In the FIB microsampling method, an FIB device (trade name "FB2200", manufactured by Hitachi) was used, and the acceleration voltage was set to 10kV. Next, the thickness of the transparent conductive layer in the sample for cross-section observation was measured by FE-TEM observation. For FE-TEM observation, an FE-TEM device (trade name: JEM-2800, manufactured by JEOL) was used, and the acceleration voltage was set to 200kV.

The thickness of the first layer of the light-transmissive conductive layer in comparative example 5 was measured as follows: a cross-sectional observation sample was prepared from the intermediate product before the second layer was formed on the first layer, and measurement was performed by FE-TEM observation of the sample. The thickness of the second layer of the light-transmitting conductive layer in comparative example 3 was determined by subtracting the thickness of the first layer from the total thickness of the light-transmitting conductive layer in comparative example 5.

Hall mobility and carrier density

The hall mobility and the carrier density of the light-transmitting conductive layer were measured for each of the transparent conductive thin films of examples 1 to 3 and comparative examples 1 to 5. A Hall Effect measurement System (trade name "HL5500PC", manufactured by Bio-Rad) was used for the measurement. The Hall mobility (cm) obtained by the measurement was measured ² V.s) anddensity of carriers (cm) ^-3 ) The values of (A) are shown in Table 1.

Resistivity-

The resistivity of the transparent conductive layers after the heat treatment was examined for each of the transparent conductive films of examples 1 to 3 and comparative examples 1 to 5. In the heating treatment, a hot air oven was used as a heating means, and the heating temperature was 130 ℃ and the heating time was 90 minutes. After the surface resistance of the light-transmitting conductive layer was measured by the four-terminal method according to JIS K7194 (1994), the resistivity (Ω · cm) of the light-transmitting conductive layer was determined by multiplying the surface resistance by the thickness of the light-transmitting conductive layer (the resistivity of the light-transmitting conductive layer in comparative example 1 could not be measured because the light-transmitting conductive layer was not crystallized by the heat treatment). The results are shown in table 1.

Crystallization rate

The crystallization rates of the transparent conductive layers of examples 1 to 3 and comparative examples 1 to 5 were examined. Specifically, first, two kinds of samples (a first sample and a second sample) are prepared for each transparent conductive film. The first sample was prepared by heat-treating the transparent conductive film at 140 ℃ for 30 minutes. A second sample was prepared by heat treating the transparent conductive film at 140 ℃ for 60 minutes. Subsequently, the sample was immersed in 5 mass% hydrochloric acid at 35 ℃ for 15 minutes. Subsequently, the sample was washed with water and dried. Next, the resistance between a pair of terminals (inter-terminal resistance) spaced at a distance of 15mm was measured on the exposed plane of the transparent conductive layer of the sample. In this measurement, when the inter-terminal resistance is 10k Ω or less, it is judged that the crystallization of the transparent conductive layer is completed.

When both the first sample and the second sample have completed crystallization, the time for completion of crystallization of the light-transmissive conductive layer is 30 minutes or less, and the crystallization rate is evaluated as "excellent". When the crystallization of the first sample was not completed and the crystallization of the second sample was completed, the crystallization completion time of the light-transmitting conductive layer was more than 30 minutes and 60 minutes or less, and the crystallization rate was evaluated as good. When crystallization was not completed in both the first sample and the second sample, the crystallization completion time of the light-transmissive conductive layer exceeded 60 minutes, and the crystallization rate was evaluated as x. The evaluation results are shown in table 1.

Preservation Property

The storage stability (degree of suppressing crystallization during storage) of the amorphous light-transmissive conductive layer was examined for each of the transparent conductive films of examples 1 to 3 and comparative examples 1 to 5. Specifically, first, two kinds of samples (a third sample and a fourth sample) are prepared for each transparent conductive film. A third sample was prepared by leaving the transparent conductive film at 50 ℃ for 15 hours. The fourth sample was prepared by leaving the transparent conductive film at 80 ℃ for 6 hours. Next, the sample was subjected to a heat treatment (crystallization of the transparent conductive layer) in a hot air oven. The heating temperature was set at 130 ℃ and the heating time was set at 90 minutes. Next, the surface of the light-transmitting conductive layer in the sample was observed with an optical microscope to confirm the presence or absence of cracks (magnification was 100 times, observation range was 2cm × 2 cm).

The transparent conductive films were evaluated as excellent in storage stability when no crack was observed in the transparent conductive layers of both the third and fourth samples. The case where cracks were observed in the transparent conductive layer of either the third sample or the fourth sample was evaluated as "o", and the case where cracks were observed in the transparent conductive layer of both the third sample and the fourth sample was evaluated as "x". The evaluation results are shown in table 1.

Confirmation of Kr atom in light-transmissive conductive layer

It was confirmed that each of the light-transmissive conductive layers in examples 1 to 3 and comparative example 1 contains Kr atoms by the following procedure. First, using a scanning fluorescent X-ray analyzer (trade name "ZSX primus iv", manufactured by korea 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 prepare an X-ray spectrum. In the prepared X-ray spectrum, it was confirmed that a peak appeared in the vicinity of the scanning angle of 28.2 °, and thus it was confirmed that Kr atoms were contained in the light-transmitting conductive layer.

< measurement conditions >

Spectrum: kr-KA

And (3) measuring the diameter: 30mm

Atmosphere: vacuum

Target: rh

Tube voltage: 50kV

Tube current: 60mA

Primary filter: ni40

Scan angle (deg): 27.0 to 29.5

Step size (step) (deg): 0.020

Speed (deg/min): 0.75

An attenuator: 1/1

Slit: s2

Spectroscopic crystal: liF (200)

A detector: SC (Single chip computer)

PHA：100～300

[ Table 1]

[ evaluation ]

In each of the transparent conductive thin films of examples 1 to 3, the light-transmitting conductive layer contained Kr, and the carrier density of the light-transmitting conductive layer was 40 × 10 ¹⁹ cm ^-3 The above. In each of the transparent conductive films of examples 1 to 3, a high crystallization rate was achieved in the light-transmitting conductive layer, and good storage stability was ensured. In contrast, the transparent conductive thin film of comparative example 1 (the carrier density of the light-transmitting conductive layer was less than 40 × 10) ¹⁹ cm ^-3 ) And comparative examples 2 and 3 (the light-transmitting conductive layer did not contain Kr, and the carrier density of the layer was 40X 10) ¹⁹ cm ^-3 As described above) and comparative examples 4 and 5 (the light-transmitting conductive layer does not contain Kr, and the carrier density of the layer is less than 40 × 10 ¹⁹ cm ^-3 ) A high crystallization rate and good storage stability cannot be achieved at the same time.

Industrial applicability

The transparent conductive thin film of the present invention is useful as a material for supplying a conductor film used for patterning a transparent electrode in various devices such as a liquid crystal display, a touch panel, and an optical sensor.

Description of the reference numerals

X transparent conductive film

D thickness direction

10. Transparent substrate

11. Resin film

12. Functional layer

20. Light-transmitting conductive layer

Claims

1. A transparent conductive film comprising a transparent substrate and an amorphous light-transmitting conductive layer in this order along the thickness direction,

the light-transmitting conductive layer contains krypton and has a size of 40 × 10 ¹⁹ cm ^-3 The above carrier density.

2. The transparent conductive film according to claim 1, wherein the light-transmissive conductive layer contains a conductive oxide containing indium.

3. The transparent conductive film according to claim 1 or 2, wherein the light-transmitting conductive layer has a thickness of 30nm or more.

4. The transparent conductive film according to any one of claims 1 to 3, wherein the light-transmissive conductive layer has 18cm ² A Hall mobility of/V.s or less.

5. The transparent conductive film according to any one of claims 1 to 4, wherein the light-transmitting conductive layer has a thickness of 2.2 x 10 after heat treatment at 130 ℃ for 1.5 hours ^-4 Resistivity of not more than Ω · cm.