Method for manufacturing a transparent conductive film

Abstract

The method for manufacturing a transparent conductive film of the present invention includes: a preparation step of preparing a transparent substrate (10); and a film formation step of forming an amorphous light-transmissive conductive layer (20) by sputtering a light-transmissive conductive material on the transparent substrate (10). In the sputtering method of the film formation step, a sputtering gas containing a rare gas having an atomic number larger than that of argon is used, and the light-transmissive conductive material is formed under a condition that a film formation gas pressure is 0.04 Pa or more and 0.9 Pa or less.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for manufacturing a transparent conductive film. BACKGROUND

[0002] Conventionally, a transparent conductive film sequentially provided with a transparent base material film and a transparent conductive layer (light-transmissive conductive layer) along the thickness direction is known. The light-transmissive conductive layer is used as, for example, a conductor film for pattern forming a transparent electrode in various devices such as liquid crystal displays, touch panels, and light sensors. In addition, the light-transmissive conductive layer is sometimes used as an antistatic layer provided in a device. The light-transmissive conductive layer is formed by, for example, forming a conductive oxide on a base material film by a sputtering method. In the sputtering method, conventionally, as a sputtering gas for colliding with a target (film formation material supply material) to cause atoms on the surface of the target to be ejected, a non-active gas such as argon is used. With respect to related art of such a transparent conductive film, it is described in, for example, Patent Document 1.

[0003] PRIOR ART DOCUMENTS

[0004] PATENT DOCUMENTS

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 5-334924 SUMMARY

[0006] Problem to be solved by the invention

[0007] The light-transmissive conductive layer of the transparent conductive film is required to have low resistance. This requirement is particularly high in the case of a transparent electrode application.

[0008] On the other hand, in the process of manufacturing the transparent conductive film and the process of manufacturing a device provided with the film, the transparent conductive film sometimes undergoes a heating process (a process of raising the temperature and then lowering the temperature). In this case, a crack sometimes occurs in the light-transmissive conductive layer due to a difference in dimensional change rate between the base material film and the light-transmissive conductive layer in the transparent conductive film. From the viewpoint of the manufacturing yield of the transparent conductive film and the viewpoint of the manufacturing yield of a device provided with the transparent conductive film, it is not preferable that a crack occurs in the light-transmissive conductive layer.

[0009] The present application provides a method for manufacturing a transparent conductive film suitable for obtaining a transparent conductive film provided with a light-transmissive conductive layer in which the generation of a crack is suppressed and the resistance is low.

[0010] Solution for solving the problem

[0011] The present invention [1] includes a method for manufacturing a transparent conductive film, comprising: a preparation step, wherein a transparent substrate is prepared; and a film forming step, wherein a light-transmitting conductive material is formed on the aforementioned transparent substrate by sputtering to form an amorphous light-transmitting conductive layer, wherein in the aforementioned sputtering method of the aforementioned film forming step, a sputtering gas containing a rare gas with an atomic number greater than that of argon is used, and the aforementioned light-transmitting conductive material is formed under the condition that the film forming gas pressure is 0.04 Pa or more and 0.9 Pa or less.

[0012] The present invention [2] includes a method for manufacturing a transparent conductive film as described in [1] above, wherein the aforementioned rare gas is krypton and / or xenon.

[0013] The present invention [3] includes a method for manufacturing a transparent conductive film as described in [1] or [2] above, wherein the krypton content in the aforementioned sputtering gas is 50% by volume or more.

[0014] The present invention [4] includes a method for manufacturing a transparent conductive film as described in any one of [1] to [3] above, wherein the aforementioned transparent conductive layer, after being heat-treated at 155°C for 1 hour, has a density of 2×10⁻⁶. -4 Resistivity below Ω·cm.

[0015] The present invention [5] includes a method for manufacturing a transparent conductive film as described in any one of [1] to [4] above, which further includes a step of heating the aforementioned transparent conductive layer to crystallize it.

[0016] The present invention [6] includes a method for manufacturing a transparent conductive film as described in any one of [1] to [5] above, and further includes a step of patterning the aforementioned transparent conductive layer.

[0017] Effects of the invention

[0018] In the method for manufacturing the transparent conductive thin film of the present invention, a sputtering gas containing a rare gas with an atomic number greater than argon is used in the sputtering process of the film formation step, and a transparent conductive material is formed under a film formation pressure of 0.04 Pa or more and 0.9 Pa or less to form an amorphous transparent conductive layer. This manufacturing method is suitable for obtaining a transparent conductive thin film with a crystalline transparent conductive layer that suppresses crack formation and has low electrical resistance. Attached Figure Description

[0019] Figure 1 This is a process diagram illustrating one embodiment of the method for manufacturing the transparent conductive film of the present invention. Figure 1 The letter A indicates the process of preparing the transparent substrate. Figure 1 The letter B indicates the process of forming a light-transmitting conductive layer on a transparent substrate.Figure 1 C indicates a process of crystallizing the light-transmissive conductive layer.

[0020] Figure 2 indicates Figure 1 a modification of the process of forming the light-transmissive conductive layer shown in B.

[0021] Figure 3 indicates the patterning process when the manufacturing method of the transparent conductive film further includes a process of patterning the light-transmissive conductive layer.

[0022] Figure 4 is a graph indicating the relationship between the amount of oxygen introduced when the light-transmissive conductive layer is formed by the sputtering method and the surface resistance of the formed light-transmissive conductive layer. DETAILED DESCRIPTION

[0023] Figure 1 is a process diagram of one embodiment of the manufacturing method of the transparent conductive film of the present application. In the present embodiment, the manufacturing method includes a preparation process, a film formation process, and a crystallization process. The manufacturing method is preferably implemented by a roll-to-roll method.

[0024] First, in the preparation process, as shown in A of Figure 1 , a transparent substrate 10 is prepared.

[0025] In the present embodiment, the transparent substrate 10 has a transparent resin film 11 and a functional layer 12 in this order toward one side of the thickness direction D. The transparent substrate 10 has a shape extending in a direction (a surface direction) orthogonal to the thickness direction D. When the manufacturing method is implemented by a roll-to-roll method, the transparent substrate 10 has an elongated shape.

[0026] The transparent resin film 11 is a transparent resin film having flexibility. As the material of the transparent resin film 11, for example, a polyester resin, a polyolefin resin, an acrylic resin, a polycarbonate resin, a polyether sulfone resin, a polyarylate resin, a melamine resin, a polyamide resin, a polyimide resin, a cellulose resin, and a polystyrene resin can be listed. As the polyester resin, for example, polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate can be listed. As the polyolefin resin, for example, polyethylene, polypropylene, and a cyclic olefin polymer can be listed. As the acrylic resin, for example, polymethyl acrylate can be listed. As the material of the transparent resin film 11, from the viewpoint of, for example, transparency and strength, a polyester resin is preferably used, and PET is more preferably used.

[0027] The functional layer 12 side surface of the transparent resin film 11 can be subjected to 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 listed.

[0028] The thickness of the transparent 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 transparent 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 transparent resin film 11 are suitable for ensuring the handleability of the transparent conductive film X to be described later, which is manufactured by the present production method.

[0029] The total light transmittance (JIS K 7375-2008) of the transparent 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 the transparency required for the transparent conductive film X in the case where the transparent conductive film X is provided in a contact sensor, a light modulation element, a photoelectric conversion element, a heat wire 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 resin film 11 is, for example, 100% or less.

[0030] In the present embodiment, the functional layer 12 is located on one face of the transparent resin film 11 in the thickness direction D. In addition, in the present embodiment, the functional layer 12 is a hard coat layer for making it difficult to form scratches on the surface of the light-transmissive conductive layer 20 to be described later, which is provided in the transparent conductive film X. Figure 1 In B of the present embodiment and C of the present embodiment, the upper surface Figure 1 In B of the present embodiment and C of the present embodiment, the upper surface

[0031] The hard coat layer is a cured product of a curable resin composition. As the resin contained in the curable resin composition, for example, a polyester resin, an acrylic resin, a urethane resin, an amide resin, a silicone resin, an epoxy resin, and a melamine resin can be cited. In addition, as the curable resin composition, for example, an ultraviolet-curable resin composition and a thermally curable resin composition can be cited. From the viewpoint that the curing occurs without high-temperature heating, which is conducive to improving the production efficiency of the transparent conductive film X, as the curable resin composition, an ultraviolet-curable resin composition is preferably used. As the ultraviolet-curable resin composition, specifically, the composition for forming a hard coat layer described in Japanese Patent Application Publication No. 2016-179686 can be cited.

[0032] The functional layer 12 as the hard coat layer can be formed by applying a curable resin composition on the transparent 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 aforementioned coating film is cured by ultraviolet irradiation. When the curable resin composition contains a thermally curable resin, the aforementioned coating film is cured by heating.

[0033] The exposed surface (the upper surface in the case of A of Figure 1 The exposed surface (the upper surface in the case of A of

[0034] The thickness of the functional layer 12 as a hard coat layer is preferably 0.1 μm or more, more preferably 0.5 μm or more. Such a configuration is suitable for causing 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.

[0035] 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, 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, particularly preferably 80 μm or less. Such a configuration relating to the thickness of the transparent substrate 10 is suitable for ensuring the handleability of the transparent conductive film X.

[0036] The total light transmittance (JIS K 7375-2008) of the transparent substrate 10 is preferably 60% or more, more preferably 80% or more, further preferably 85% or more. Such a configuration is suitable for ensuring the transparency required of the transparent conductive film X in the case where the transparent conductive film X is provided in a touch sensor, a light modulation element, a photoelectric conversion element, a heat wire 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.

[0037] Next, in a film formation step, as shown in B of Figure 1 The light-transmissive conductive layer 20 is formed by film formation of a light-transmissive conductive material on one surface of the functional layer 12 in the thickness direction D of the transparent substrate 10 using a sputtering method. The light-transmissive conductive layer 20 has a shape extending in the surface direction on the transparent substrate 10. The light-transmissive conductive layer 20 has both light transmittance and conductivity.

[0038] In the sputtering method, a sputtering film formation device capable of implementing a film formation process using a roll-to-roll system is preferably used. When a sputtering film formation device using a roll-to-roll system is used, in the film formation step, the long strip-shaped transparent substrate 10 is caused to travel from a discharge roll provided in the device to a take-up roll, and a material is film-formed on the transparent substrate 10 to form the light-transmissive conductive layer 20. In this sputtering method, a sputtering film formation device provided with one film formation chamber can be used, or a sputtering film formation device provided with a plurality of film formation chambers arranged in series along the travel path of the transparent substrate 10 can be used.

[0039] In the sputtering method, specifically, after vacuum exhaust is performed in a film formation chamber provided in a sputtering film formation apparatus, a negative voltage is applied to a target (light-transmissive conductive material supply material) provided on a cathode in the film formation chamber while a sputtering gas (non-reactive gas) is introduced into the film formation chamber. As a result of this, glow discharge is generated to ionize gas atoms, and the gas ions collide with the surface of the target at high speed to cause the target material to be ejected from the surface of the target, and the ejected target material is accumulated on the functional layer 12 in the transparent substrate 10 as the light-transmissive conductive material.

[0040] As the sputtering gas, a non-reactive gas containing a rare gas having an atomic number larger than that of argon (Ar) is used. As the rare gas having an atomic number larger than that of Ar, for example, krypton (Kr), xenon (Xe), and radon (Rn) can be listed, and Kr and / or Xe is preferably used. From the viewpoint of the manufacturing cost of the transparent conductive thin film X, as the sputtering gas, Kr is preferably used. When the sputtering gas contains Kr, the proportion of Kr in the sputtering gas is, for example, 1% by volume or more, preferably 50% by volume or more, more preferably 99% by volume or more, further preferably 99.5% by volume or more, and particularly preferably 99.9% by volume or more. The proportion is, for example, 100% by volume or less. In addition, the sputtering gas can contain other non-reactive gases (non-reactive gases other than the rare gas having an atomic number larger than that of Ar) such as Ar.

[0041] The sputtering method is preferably a reactive sputtering method. In the reactive sputtering method, a reactive gas is introduced into the film formation chamber in addition to the sputtering gas. When the conductive oxide described later is used as the light-transmissive conductive material, as the reactive gas, oxygen is preferably used. The proportion of the flow rate of the reactive gas such as oxygen used in the reactive sputtering method with respect to the total flow rate of the sputtering gas (non-reactive gas) and the reactive gas is preferably 0.01 flow% or more, more preferably 0.05 flow% or more, and further preferably 0.08 flow% or more. The proportion of the flow rate is, for example, 15 flow% or less, preferably 8 flow% or less, more preferably 6 flow% or less, and further preferably 4 flow% or less.

[0042] The gas pressure (film formation gas pressure) in the film formation chamber in which the gas (in the reactive sputtering method, the sputtering gas and the reactive gas) is introduced after vacuum exhaust is 0.04 Pa or more, preferably 0.08 Pa or more, and more preferably 0.1 Pa or more. The film formation gas pressure is 0.9 Pa or less, preferably 0.8 Pa or less, and more preferably 0.7 Pa or less.

[0043] The temperature of the transparent substrate 10 in this process (film formation temperature) is, for example, 100°C or lower, preferably 50°C or lower, more preferably 30°C or lower, further preferably 25°C or lower, still further preferably 20°C or lower, particularly preferably 15°C or lower, yet further preferably 10°C or lower, most preferably 5°C or lower, and, in addition, for example, -50°C or higher, preferably -20°C or higher, more preferably -10°C or higher, further preferably -7°C or higher.

[0044] As the power source for applying a voltage to the target, for example, a DC power source, an AC power source, an MF power source, and an RF power source can be listed. As the power source, a DC power source and an RF power source can be used in combination. The absolute value of the discharge voltage in sputter film formation is, for example, 50 V or higher, and, in addition, for example, 500 V or lower. The horizontal magnetic field strength on the surface of the target is, for example, 10 mT or higher, preferably 20 mT or higher, more preferably 30 mT or higher, further preferably 60 mT or higher, and, in addition, for example, 300 mT or lower, preferably 250 mT or lower. Such a configuration is preferable in terms of suppressing the amount of impurities in the light-transmissive conductive layer 20. Suppression of the amount of impurities in the light-transmissive conductive layer 20 contributes to low resistance of the light-transmissive conductive layer 20, and, in addition, contributes to suppression of crack generation in the light-transmissive conductive layer 20 in a heating process.

[0045] As the light-transmissive conductive material, for example, a conductive oxide can be listed. As the conductive oxide, for example, a metal oxide 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 can be listed. Specifically, as the conductive oxide, indium tin composite oxide (ITO), indium zinc composite oxide (IZO), indium gallium composite oxide (IGO), indium gallium zinc composite oxide (IGZO), and antimony tin composite oxide (ATO) can be listed. From the viewpoint of achieving high transparency and good conductivity in the light-transmissive conductive layer 20, as the conductive oxide, indium tin composite oxide (ITO) containing both In and Sn is preferably used. The ITO can contain a metal or semimetal other than In and Sn in an amount smaller than the content of each of In and Sn.

[0046] When ITO is used as the conductive oxide, the proportion of the content of tin oxide in the light-transmissive conductive layer 20 with respect to the total content of indium oxide (In203) and tin oxide (Sn02) is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more. This configuration is suitable for ensuring the durability of the light-transmissive conductive layer 20. In addition, from the viewpoint of obtaining a crystalline light-transmissive conductive layer 20 that easily crystallizes due to heating, the above proportion of the content of tin oxide is preferably 15% by mass or less, more preferably 13% by mass or less, and further preferably 12% by mass or less. The above proportion of the content of tin oxide can be adjusted by adjusting the concentration of tin oxide in the ITO target used in the sputtering method. The ratio of the number of tin atoms to the number of indium atoms in the ITO is found by, for example, determining the presence ratio of indium atoms and tin atoms using X-ray Photoelectron Spectroscopy (XPS) on the object of measurement. The above proportion of the content of tin oxide in the ITO is found from the presence ratio of indium atoms and tin atoms determined in this manner. The above proportion of the content of tin oxide in the ITO can be determined from the proportion of the content of tin oxide (Sn02) in the ITO target used when the film is formed by sputtering.

[0047] The proportion of the content of tin oxide in the light-transmissive conductive layer 20 can be different in the thickness direction D. For example, as shown in FIG. 2, the light-transmissive conductive layer 20 can have a first region 21 in which the proportion of the content of tin oxide with respect to the total content of tin oxide and indium oxide is relatively large, and a second region 22 in which the proportion of the content of tin oxide with respect to the total content of tin oxide and indium oxide is relatively small, in this order from the transparent substrate 10 side. Figure 2 The proportion of the content of tin oxide in the light-transmissive conductive layer 20 can be different in the thickness direction D. For example, as shown in FIG. 2, the light-transmissive conductive layer 20 can have a first region 21 in which the proportion of the content of tin oxide with respect to the total content of tin oxide and indium oxide is relatively large, and a second region 22 in which the proportion of the content of tin oxide with respect to the total content of tin oxide and indium oxide is relatively small, in this order from the transparent substrate 10 side. The proportion of the content of tin oxide in the light-transmissive conductive layer 20 can be different in the thickness direction D. For example, as shown in FIG. 2, the light-transmissive conductive layer 20 can have a first region 21 in which the proportion of the content of tin oxide with respect to the total content of tin oxide and indium oxide is relatively large, and a second region 22 in which the proportion of the content of tin oxide with respect to the total content of tin oxide and indium oxide is relatively small, in this order from the transparent substrate 10 side.

[0048] When the light-transmissive conductive layer 20 includes the first region 21 and the second region 22, the thickness of the first region 21 with respect to the total thickness of the first region 21 and the second region 22 is preferably more than 50%, more preferably 60% or more, and further preferably 64% or more. The ratio is less than 100%. In addition, the thickness of the second region 22 with respect to the total thickness of the first region 21 and the second region 22 is preferably less than 50%, more preferably 40% or less, and further preferably 36% or less. This configuration relating to the thickness ratio of each of the first region 21 and the second region 22 is preferable from the viewpoint of achieving a low resistivity of the crystallized light-transmissive conductive layer 20. In Figure 2 In the present embodiment, although the boundary between the first region 21 and the second region 22 is depicted by a broken line, the boundary between the first region 21 and the second region 22 is not always clear when there is no significant difference in the composition of the first region 21 and the second region 22.

[0049] Alternatively, in the light-transmissive conductive layer 20, the proportion of tin oxide in the thickness direction D can gradually change. For example, in the light-transmissive conductive layer 20, the proportion of tin oxide in the thickness direction D can increase or decrease as it moves away from the transparent substrate 10. In the light-transmissive conductive layer 20, a region in which the proportion of tin oxide increases as it moves away from the transparent substrate 10 can be located on the side of the transparent substrate 10, and a region in which the proportion of tin oxide decreases as it moves away from the transparent substrate 10 can be located on the side opposite the transparent substrate 10. In the light-transmissive conductive layer 20, a region in which the proportion of Kr decreases as it moves away from the transparent substrate 10 can be located on the side of the transparent substrate 10, and a region in which the proportion of Kr increases as it moves away from the transparent substrate 10 can be located on the side opposite the transparent substrate 10.

[0050] The light-transmissive conductive layer 20 can contain a rare gas atom having an atomic number larger than Ar (a rare gas atom such as Kr used as a sputtering gas). The light-transmissive conductive layer 20 contains, at least in part in the thickness direction D, a region in which the content ratio of the rare gas atom (Kr or the like) having an atomic number larger than Ar is preferably 1.0 atomic% or less, more preferably 0.7 atomic% or less, further preferably 0.5 atomic% or less, more further preferably 0.3 atomic% or less, particularly preferably 0.2 atomic% or less, and especially preferably less than 0.1 atomic%. The content ratio of the rare gas atom having an atomic number larger than Ar in the region is, for example, 0.0001 atomic% or more. The light-transmissive conductive layer 20 preferably satisfies the above content ratio of the rare gas atom having an atomic number larger than Ar in the entire region in the thickness direction D. Specifically, the content ratio of the rare gas atom (Kr or the like) having an atomic number larger than Ar in the light-transmissive conductive layer 20 is preferably 1.0 atomic% or less, more preferably 0.7 atomic% or less, further preferably 0.5 atomic% or less, more further preferably 0.3 atomic% or less, particularly preferably 0.2 atomic% or less, and especially preferably less than 0.1 atomic% in the entire region in the thickness direction D. These configurations are suitable for achieving good crystal growth, forming large crystal grains, at the time of heating for crystallizing the light-transmissive conductive layer 20, and thus are suitable for obtaining a low-resistance and crystalline light-transmissive conductive layer 20 (the larger the crystal grains in the crystalline light-transmissive conductive layer 20, the lower the resistance of the light-transmissive conductive layer 20).

[0051] As to whether the rare gas atom is present in the light-transmissive conductive layer 20, for example, the presence of the rare gas atom is identified by the fluorescent X-ray analysis described later in the examples. In addition, as to whether the rare gas atom is present in the light-transmissive conductive layer 20 and the content thereof, for example, the presence of the rare gas atom is identified by Rutherford Backscattering Spectrometry. As to whether the rare gas atom such as Kr is present in the light-transmissive conductive layer 20, for example, the presence of the rare gas atom is identified by the fluorescent X-ray analysis described later in the examples. In the case where the content of the rare gas atom is not more than the detection limit (lower limit) and the presence of the rare gas atom is identified by the fluorescent X-ray analysis, it is determined that the light-transmissive conductive layer contains a region in which the content ratio of the rare gas atom such as Kr is 0.0001 atomic% or more.

[0052] In the film formation step, the amorphous light-transmissive conductive layer 20 is formed as described above. By adjusting the film formation temperature and / or adjusting the flow rate ratio of the reactive gas, it is possible to form the amorphous light-transmissive conductive layer 20.

[0053] Whether the light-transmissive conductive layer is amorphous or crystalline can be determined by, for example, the following operation. First, the light-transmissive conductive layer (the light-transmissive conductive layer 20 on the transparent substrate 10 in the transparent conductive film X) is immersed in 5 mass% hydrochloric acid at 20°C for 15 minutes (hydrochloric acid treatment). Next, the light-transmissive conductive layer is washed with water and then dried. Next, the resistance between a pair of terminals spaced apart by 15 mm (terminal-to-terminal resistance) is measured in the exposed plane of the light-transmissive conductive layer (the surface of the light-transmissive conductive layer 20 on the side opposite the transparent substrate 10 in the transparent conductive film X). In this measurement, when the terminal-to-terminal resistance exceeds 10 kΩ, the light-transmissive conductive layer is amorphous (the light-transmissive conductive layer 20 after the film formation step and after the crystallization step described below is amorphous, which can be determined based on this criterion). In addition, in this measurement, when the terminal-to-terminal resistance is 10 kΩ or less, the light-transmissive conductive layer is crystalline (the light-transmissive conductive layer 20 after the crystallization step described below is crystalline, which can be determined based on this criterion).

[0054] The thickness of the amorphous light-transmissive conductive layer 20 is, for example, 10 nm or more, preferably 40 nm or more, more preferably more than 40 nm, further preferably 70 nm or more, still further preferably 100 nm or more, and particularly preferably 130 nm or more. Such a configuration is suitable for achieving low resistance of the light-transmissive conductive layer 20 after crystallization. In addition, the thickness of the light-transmissive conductive layer 20 is preferably 1000 nm or less, more preferably 250 nm or less, further preferably 200 nm or less, particularly preferably 160 nm or less, and most preferably less than 150 nm. Such a configuration is suitable for suppressing warping of the transparent conductive film X manufactured.

[0055] The surface resistance of the amorphous light-transmissive conductive layer 20 is, for example, 800 Ω / D or less, preferably 100 Ω / D or less, more preferably 50 Ω / D or less, further preferably 15 Ω / D or less, and particularly preferably 13 Ω / D or less. The surface resistance of the amorphous light-transmissive conductive layer 20 is, for example, 1 Ω / D or more. The surface resistance can be measured by the four-terminal method based on JIS K7194. The surface resistance of the amorphous light-transmissive conductive layer 20 can be controlled by, for example, adjusting the film formation temperature in the film formation step and / or adjusting the flow rate ratio of the reactive gas.

[0056] The resistivity of the amorphous light-transmissive conductive layer 20 is 4 x 10 -4 Ω·cm or more, preferably 4.5 x 10 -4 Ω·cm or more, more preferably 4.8 x 10 -4 Ω·cm or more, further preferably 5 x 10 -4 Ω·cm or more, and particularly preferably 5.2 x 10 -4The resistivity is preferably 12 × 10⁻⁶ Ω·cm or higher. The amorphous, transparent conductive layer 20 has a resistivity of 12 × 10⁻⁶ Ω·cm or higher. -4 Ω·cm or less, more preferably 11×10 -4 Below Ω·cm, more preferably 10.5×10 -4 Below Ω·cm. This resistivity-related configuration is suitable for achieving low resistivity in the transparent conductive layer 20 after crystallization. The resistivity is obtained by multiplying the surface resistance by the thickness.

[0057] The resistivity of the amorphous, transparent conductive layer 20 after heat treatment at 155°C for 1 hour is preferably 2.2 × 10⁻⁶. -4 Ω·cm or less, more preferably 2.0×10 -4 Below Ω·cm, further preferably 1.9×10 -4 Below Ω·cm. This configuration is suitable for ensuring the low resistivity required for the transparent conductive layer 20 of the transparent conductive film X in applications such as contact sensors, dimming elements, photoelectric conversion elements, hot-wire control components, antenna components, electromagnetic wave shielding components, lighting devices, and image display devices that possess a transparent conductive film X. Furthermore, the resistivity of the amorphous transparent conductive layer 20 after heat treatment at 155°C for 1 hour is, for example, 0.1 × 10⁻⁶. -4 Ω·cm or higher, preferably 0.5×10 -4 Ω·cm or more, more preferably 1×10 -4 Ω·cm or higher.

[0058] The total light transmittance (JIS K 7375-2008) of the amorphous transparent conductive layer 20 is preferably 60% or more, more preferably 80% or more, and even more preferably 85% or more. This configuration is suitable for ensuring the transparency of the transparent conductive layer 20 after crystallization. Furthermore, the total light transmittance of the amorphous transparent conductive layer 20 is, for example, 100% or less.

[0059] Next, in the crystallization process, such as Figure 1 As shown in Figure C, the transparent conductive layer 20 is transformed from an amorphous material to a crystalline material (crystallization) by heating. Examples of heating methods include infrared heaters and ovens. From the viewpoint of ensuring a high crystallization rate, the heating temperature is, for example, 100°C or higher, preferably 120°C or higher. From the viewpoint of suppressing the effect of heating on the transparent substrate 10, the heating temperature is, for example, 200°C or lower, preferably 180°C or lower, more preferably 170°C or lower, and even more preferably 165°C or lower. The heating time is, for example, less than 120 minutes, preferably 90 minutes or lower, more preferably 60 minutes or lower, and also, for example, more than 1 minute, preferably more than 5 minutes.

[0060] The transparent conductive film X was produced by the above operation. The transparent conductive film X had the transparent substrate 10 and the light-transmissive conductive layer 20 having both light-transmissivity and conductivity in this order from the side of the one face of the thickness direction D. The transparent conductive film X was one element included in a contact sensor, a light control element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shielding member, an illuminating device, an image display device, and the like.

[0061] In the transparent conductive film X, the thickness of the light-transmissive conductive layer 20 after crystallization (i.e., crystalline) was, for example, the same as that of the light-transmissive conductive layer 20 of amorphous, and was, for example, 10 nm or more, preferably more than 40 nm, more preferably 70 nm or more, further preferably 100 nm or more, and particularly preferably 130 nm or more. This configuration was suitable for achieving low resistance of the light-transmissive conductive layer 20 in the transparent conductive film X. In addition, the thickness of the light-transmissive conductive layer 20 of crystalline was, for example, the same as that of the light-transmissive conductive layer 20 of amorphous, and was preferably 1000 nm or less, more preferably 250 nm or less, further preferably 200 nm or less, and particularly preferably 160 nm or less. This configuration was suitable for suppressing warping of the transparent conductive film X.

[0062] The surface resistance of the light-transmissive conductive layer 20 of crystalline was, for example, 200 Ω / D or less, preferably 100 Ω / D or less, more preferably 80 Ω / D or less, further preferably 30 Ω / D or less, and particularly preferably 20 Ω / D or less. This configuration was suitable for ensuring the low resistance required for the light-transmissive conductive layer 20 of the transparent conductive film X in the case where the transparent conductive film X was included in a contact sensor, a light control element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shielding member, an illuminating device, an image display device, and the like. The surface resistance of the light-transmissive conductive layer 20 of crystalline was, for example, 0.1 Ω / D or more.

[0063] The specific resistance of the light-transmissive conductive layer 20 of crystalline was preferably 2.2 x 10 -4 Ω·cm or less, more preferably 2 x 10 -4 Ω·cm or less, further preferably 1.9 x 10 -4 Ω·cm or less. This configuration was suitable for ensuring the low resistance required for the light-transmissive conductive layer 20 of the transparent conductive film X in the case where the transparent conductive film X was included in a contact sensor, a light control element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shielding member, an illuminating device, an image display device, and the like. The specific resistance of the light-transmissive conductive layer 20 of crystalline was, for example, 0.1 x 10 -4 Ω·cm or more, preferably 0.5 x 10 -4 Ω·cm or more, more preferably 1 x 10 -4Ω · cm or more.

[0064] The total light transmittance (JIS K 7375-2008) of the crystalline light-transmissive 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 the transparency required of the transparent conductive film X in a contact sensor, a light modulation element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shielding member, a lighting device, an image display device, or the like. The total light transmittance of the crystalline light-transmissive conductive layer 20 is, for example, 100% or less.

[0065] As Figure 3 As schematically shown in FIG. 1, the light-transmissive conductive layer 20 in the transparent conductive film X can be patterned (patterning step). The light-transmissive conductive layer 20 can be patterned by etching the light-transmissive conductive layer 20 through a prescribed etching mask. The patterned light-transmissive conductive layer 20 functions as, for example, a wiring pattern. The patterning step can be implemented before the crystallization step described above. In this case, the light-transmissive conductive layer 20 is crystallized by heating after the patterning step.

[0066] In the film formation step of the present production method, as described above in B of Figure 1 , a non-active gas containing a rare gas having an atomic number larger than that of argon is used as a sputtering gas in the sputtering method, and the light-transmissive conductive material is formed into an amorphous light-transmissive conductive layer 20 under conditions in which the film formation gas pressure is 0.04 Pa or more and 0.9 Pa or less (preferably 0.08 Pa or more, more preferably 0.1 Pa or more, and preferably 0.8 Pa or less, more preferably 0.7 Pa or less). Such a production method is suitable for obtaining a transparent conductive film X having a crystalline light-transmissive conductive layer 20 in which the generation of cracks is suppressed and the resistance is low. Specifically, as shown in the examples and comparative examples described later.

[0067] As the sputtering gas in the film formation step, as described above, Kr and / or Xe is preferably used. When the sputtering gas contains Kr, as described above, the proportion of Kr in the sputtering gas is preferably 50% by volume or more, more preferably 99% by volume or more, further preferably 99.5% by volume or more, and particularly preferably 99.9% by volume or more. These configurations related to the sputtering gas are suitable for forming a crystalline light-transmissive conductive layer 20 in which the generation of cracks is suppressed and the resistance is low from an amorphous light-transmissive conductive layer 20.

[0068] In the transparent conductive film X, the functional layer 12 can be an adhesion improvement layer for achieving high adhesion of the light-transmissive conductive layer 20 with respect to the transparent substrate 10. The constitution of the functional layer 12 as the adhesion improvement layer is suitable for ensuring the adhesion between the transparent substrate 10 and the light-transmissive conductive layer 20.

[0069] The functional layer 12 can be an index-matching layer for adjusting the reflectance of the surface (one face in the thickness direction D) of the transparent substrate 10. The constitution of the functional layer 12 as the index-matching layer is suitable for making it difficult to visually recognize the pattern shape of the light-transmissive conductive layer 20 in the case where the light-transmissive conductive layer 20 is patterned on the transparent substrate 10.

[0070] The functional layer 12 can be a peeling function layer for practically peeling the light-transmissive conductive layer 20 from the transparent substrate 10. The constitution of the functional layer 12 as the peeling function layer is suitable for peeling the light-transmissive conductive layer 20 from the transparent substrate 10 and transferring the light-transmissive conductive layer 20 to another member.

[0071] The functional layer 12 can be a composite layer in which a plurality of layers are connected in the thickness direction D. The composite layer preferably contains two or more layers selected from the group consisting of a hard coat layer, an adhesion improvement layer, an index-matching layer, and a peeling function layer. Such a constitution is suitable for making the functional layer 12 exhibit the above-described functions of the selected respective layers in a composite manner. In one preferred mode, the functional layer 12 has, on the one face side of the transparent resin film 11 in the thickness direction D, an adhesion improvement layer, a hard coat layer, and an index-matching layer in this order. In another preferred mode, the functional layer 12 has, on the one face side of the transparent resin film 11 in the thickness direction D, a peeling function layer, a hard coat layer, and an index-matching layer in this order.

[0072] The transparent conductive film X is used in a state of being attached to an article and, as necessary, the light-transmissive conductive layer 20 is patterned. The transparent conductive film X is attached to an article by, for example, fixing the functional layer.

[0073] As the article, there can be cited, for example, elements, members, and devices. That is, as the article with the transparent conductive film, there can be cited, for example, an element with the transparent conductive film, a member with the transparent conductive film, and a device with the transparent conductive film.

[0074] As the element, for example, a light adjusting element and a photoelectric conversion element can be given. As the light adjusting element, for example, a current drive type light adjusting element and an electric field drive type light adjusting element can be given. As the current drive type light adjusting element, for example, an electrochromic (EC) light adjusting element can be given. As the electric field drive type light adjusting element, for example, a PDLC (polymer dispersed liquid crystal) light adjusting element, a PNLC (polymer network liquid crystal) light adjusting element, and an SPD (suspended particle device) light adjusting element can be given. As the photoelectric conversion element, for example, a solar cell and the like can be given. As the solar cell, for example, an organic thin film solar cell and a dye-sensitized solar cell can be given. As the member, for example, an electromagnetic wave shielding member, a heat ray control member, a heater member, and an antenna member can be given. As the device, for example, a contact sensor device, an illumination device, and an image display device can be given.

[0075] As the above-described fixed function layer, for example, an adhesive layer and a bonding layer can be given. As the material of the fixed function layer, a material having transparency and exhibiting a fixed function can be used without particular limitation. The fixed function layer is preferably formed of a resin. As the resin, for example, an acrylic resin, a silicone resin, a polyester resin, a polyurethane resin, a polyamide resin, a polyvinyl ether resin, a vinyl acetate / vinyl chloride copolymer, a modified polyolefin resin, an epoxy resin, a fluorine resin, a natural rubber, and a synthetic rubber can be given. Among the aforementioned resins, an acrylic resin is preferred from the viewpoint of exhibiting cohesive properties such as cohesion, adhesion, and moderate wettability, excellent transparency, and excellent weather resistance and heat resistance.

[0076] In order to suppress corrosion of the light-transmissive conductive layer 20, an anticorrosive agent can be compounded in the fixed function layer (resin forming the fixed function layer). In order to suppress migration of the light-transmissive conductive layer 20, an antimigrating agent (for example, a material disclosed in Japanese Patent Application Publication No. 2015-022397) can be compounded in the fixed function layer (resin forming the fixed function layer). In addition, in order to suppress degradation of the article when used outdoors, an ultraviolet absorbing agent can be compounded in the fixed function layer (resin forming the fixed function layer). As the ultraviolet absorbing agent, for example, a benzophenone compound, a benzotriazole compound, a salicylic acid compound, an oxanilide compound, a cyanoacrylate compound, and a triazine compound can be given.

[0077] In addition, when the transparent substrate 10 of the transparent conductive film X is fixed to an article with the fixed function layer, the light-transmissive conductive layer 20 (including the light-transmissive conductive layer 20 after patterning) is exposed in the transparent conductive film X. In this case, a cover layer can be provided on the exposed surface of the light-transmissive conductive layer 20. The cover layer is a layer that covers the light-transmissive conductive layer 20, and can improve the reliability of the light-transmissive conductive layer 20, and can suppress functional deterioration due to damage to the light-transmissive conductive layer 20. The cover layer is preferably formed of a dielectric material, and more preferably formed of a composite material of a resin and an inorganic material. As the resin, for example, the resins described above with respect to the fixed function layer can be cited. As the inorganic material, for example, inorganic oxides and fluorides can be cited. As the inorganic oxides, for example, silicon oxide, titanium oxide, niobium oxide, aluminum oxide, zirconium dioxide, and calcium oxide can be cited. As the fluorides, for example, magnesium fluoride can be cited. In addition, the above-mentioned corrosion inhibitor, anti-migration agent, and ultraviolet absorber can be compounded in the cover layer (mixture of resin and inorganic material).

[0078] Example

[0079] With respect to the present application, the following example is shown to be specifically described. The present application is not limited to the example. In addition, the specific numerical values of the compounding amount (content), physical property value, parameter, and the like described below can be replaced with the upper limit (numerical value defined in the form of "to" or "less than") or lower limit (numerical value defined in the form of "to" or "more than") of the compounding amount (content), physical property value, parameter, and the like corresponding thereto described in the above "DETAILED DESCRIPTION OF THE INVENTION".

[0080] [Example 1]

[0081] On one face of a long strip of PET film (thickness 50 μm, manufactured by Mitsubishi Chemical Corporation) as a transparent resin film, an ultraviolet-curable resin containing an acrylic resin was applied to form a coating film. Next, the coating film was cured by ultraviolet irradiation to form a hard coat layer (thickness 2 μm). In this way, a transparent substrate having a transparent resin film and a hard coat layer as a function layer was produced.

[0082] Next, a light-transmissive conductive layer was formed on the hard coat layer in the transparent substrate by a reactive sputtering method. In the reactive sputtering method, a sputtering film forming device capable of performing a film forming process by a roll-to-roll system was used. The sputtering film forming device was a DC magnetron sputtering device provided with a first film forming chamber (film forming chamber on the upstream side) and a second film forming chamber (film forming chamber on the downstream side) arranged in this order along the traveling path of the transparent substrate. By film formation (first sputtering film formation) based on the reactive sputtering method in the first film forming chamber, a first region of the light-transmissive conductive layer was formed on the transparent substrate, and by film formation (second sputtering film formation) based on the reactive sputtering method in the second film forming chamber, a second region of the light-transmissive conductive layer was formed on the first region.

[0083] The first sputtering film formation conditions are shown below. As the target, a first target was used, which was a sintered body of indium oxide and tin oxide (ITO with a tin oxide concentration of 10 mass%). The power source for applying voltage to the target was a DC power source. The horizontal magnetic field strength on the target was set to 90 mT. The film formation temperature (the temperature of the transparent substrate on which the transparent conductive layer was to be layered) was set to -5°C. In addition, the first film formation chamber was vacuum evacuated until the degree of vacuum inside the first film formation chamber reached 0.9 x 10 -4 After the degree of vacuum reached 0.9 x 10 Figure 4 The oxygen introduction amount was adjusted in such a way that the value of the surface resistance of the formed film reached 50 Ω / D within the region R of the surface resistance-oxygen introduction amount curve as shown in FIG. 1. Figure 4 The surface resistance-oxygen introduction amount curve shown in FIG. 1 can be made by previously investigating the oxygen introduction amount dependency of the surface resistance of the transparent conductive layer when the transparent conductive layer is formed by the reactive sputtering method under the same conditions as the above except for the oxygen introduction amount.

[0084] In the second sputtering film formation, as the target, a second target was used, which was a sintered body of indium oxide and tin oxide (ITO with a tin oxide concentration of 3 mass%). The other conditions in the second sputtering film formation were the same as in the first sputtering film formation.

[0085] The transparent conductive thin film of Example 1 was made by the above operations. The transparent conductive layer (thickness 100 nm, amorphous) of the transparent conductive thin film of Example 1 had, from the transparent substrate side, a first region (thickness 95 nm) formed of ITO containing Kr (tin oxide concentration 10 mass%) and a second region (thickness 5 nm) formed of ITO containing Kr (tin oxide concentration 3 mass%) in this order.

[0086] [Examples 2 to 5]

[0087] In the first sputtering film formation and the second sputtering film formation, the degree of vacuum inside each film formation chamber was set to 0.2 Pa (Example 2), 0.4 Pa (Example 3), 0.6 Pa (Example 4), or 0.8 Pa (Example 5) instead of 0.1 Pa, and otherwise, the same operations as for the transparent conductive thin film of Example 1 were performed to make each of the transparent conductive thin films of Examples 2 to 5.

[0088] [Example 6]

[0089] In the first sputter film formation, the gas pressure was set to 0.2 Pa instead of 0.1 Pa, and the thickness of the first region formed was set to 142 nm instead of 95 nm, and, in the second sputter film formation, the gas pressure was set to 0.2 Pa instead of 0.1 Pa, and the thickness of the second region formed was set to 8 nm instead of 5 nm, and, other than that, the same operations as in the transparent conductive film of Example 1 were performed to produce the transparent conductive film of Example 6. The total thickness of the light-transmissive conductive layer of this transparent conductive film was 150 nm.

[0090] [Example 7]

[0091] In the first sputter film formation, the gas pressure was set to 0.2 Pa instead of 0.1 Pa, and the thickness of the first region formed was set to 38 nm instead of 95 nm, and, in the second sputter film formation, the gas pressure was set to 0.2 Pa instead of 0.1 Pa, and the thickness of the second region formed was set to 2 nm instead of 5 nm, and, other than that, the same operations as in the transparent conductive film of Example 1 were performed to produce the transparent conductive film of Example 7. The total thickness of the light-transmissive conductive layer of this transparent conductive film was 40 nm.

[0092] [Example 8]

[0093] In the second sputter film formation, as the sputter gas, Ar was used instead of Kr, and the above-mentioned first target (ITO with a tin oxide concentration of 10 mass%) was used instead of the second target, and, other than that, the same operations as in the transparent conductive film of Example 2 were performed to produce the transparent conductive film of Example 8.

[0094] [Example 9]

[0095] In the first sputter film formation and the second sputter film formation, as the sputter gas, a mixed gas of Kr and Ar (volume ratio of the mixed gas: Kr:Ar = 95:5) was used instead of Kr, and, other than that, the same operations as in the transparent conductive film of Example 2 were performed to produce the transparent conductive film of Example 9.

[0096] [Comparative Example 1]

[0097] In the first sputter film formation and the second sputter film formation, the gas pressure in each film formation chamber was set to 1.0 Pa instead of 0.1 Pa, and, other than that, the same operations as in the transparent conductive film of Example 1 were performed to produce the transparent conductive film of Comparative Example 1.

[0098] [Comparative Examples 2 to 4]

[0099] In the first sputtering film formation and the second sputtering film formation, Ar was used instead of Kr as the sputtering gas, and otherwise, the same operations as in the transparent conductive film of Example 2 were performed to produce the transparent conductive film of Comparative Example 2, the same operations as in the transparent conductive film of Example 5 were performed to produce the transparent conductive film of Comparative Example 3, and the same operations as in the transparent conductive film of Comparative Example 1 were performed to produce the transparent conductive film of Comparative Example 4.

[0100] 〈Thickness of light-transmissive conductive layer〉

[0101] The thickness of each light-transmissive conductive layer in Examples 1 to 9 and Comparative Examples 1 to 4 was measured by FE-TEM observation. Specifically, first, a cross-sectional observation sample of each light-transmissive conductive layer in Examples 1 to 9 and Comparative Examples 1 to 4 was produced by FIB microsampling. In the FIB microsampling, an FIB device (trade name: "FB2200", manufactured by Hitachi, Ltd.) was used, and the acceleration voltage was set to 10 kV. Next, the thickness of the light-transmissive conductive layer in the cross-sectional observation sample was measured by FE-TEM observation. In the FE-TEM observation, an FE-TEM device (trade name: "JEM-2800", manufactured by JEOL Ltd.) was used, and the acceleration voltage was set to 200 kV.

[0102] In addition, the thickness of the first region of each light-transmissive conductive layer was measured by producing a cross-sectional observation sample from an intermediate product before the second region was formed on the first region and by FE-TEM observation of the sample. The thickness of the second region of each light-transmissive conductive layer was obtained by subtracting the thickness of the first region from the total thickness of the light-transmissive conductive layer.

[0103] 〈Surface resistance and resistivity〉

[0104] Regarding each light-transmissive conductive layer in Examples 1 to 9 and Comparative Examples 1 to 4, the resistivity after heat treatment in a hot-air oven was investigated. In the heat treatment, the heating temperature was set to 155°C, and the heating time was set to 1 hour. After the surface resistance (surface resistance R1) of the light-transmissive conductive layer was measured by the four-terminal method based on JIS K 7194 (1994), the resistivity (resistivity R2) was obtained by multiplying the surface resistance value by the total thickness of the light-transmissive conductive layer. The values of the surface resistance R1 (Ω / □) and the resistivity R2 (Ω·cm) of each light-transmissive conductive layer are shown in Table 1 (regarding the light-transmissive conductive layer in Comparative Example 1, since a plurality of cracks were generated, accurate resistance values could not be obtained).

[0105] 〈Evaluation of suppression of cracks〉

[0106] The degree of occurrence of cracks in the light-transmissive conductive layer upon heat treatment was investigated for each of the transparent conductive films of Examples 1 to 9 and Comparative Examples 1 to 4. Specifically, first, three pieces of the transparent conductive film having a size of 50 cm in length and 5 cm in short side were prepared, and the two short sides of each film were fixed to the surface of an iron plate with heat-resistant tape. Next, each of the transparent conductive films on the iron plate was subjected to heat treatment in a hot air oven. In the heat treatment, the heating temperature was set to 140°C, and the heating time was set to 1 hour. Next, the transparent conductive film after the heat treatment was subdivided into a size of 5 cm x 5 cm to obtain 30 pieces of observation samples. Next, for each sample, observation was performed using an optical microscope, and the presence or absence of cracks was investigated. Furthermore, regarding the suppression of cracks in the transparent conductive film, the case where the number of samples in which cracks were confirmed in the light-transmissive conductive layer was 15 or less was evaluated as "O", the case where the number was 16 to 25 was evaluated as "Δ", and the case where the number was 26 or more was evaluated as "X". The same operation and evaluation as the above were performed except that the heating temperature in the heat treatment was set to 155°C or 165°C instead of 140°C. The evaluation results thereof are shown in Table 1.

[0107] <Confirmation of Kr atoms in the light-transmissive conductive layer>

[0108] Each of the light-transmissive conductive layers in Examples 1 to 9 and Comparative Examples 1 to 4 was confirmed to contain Kr atoms and Ar atoms by the following operation. First, using a scanning-type fluorescent X-ray analysis device (trade name "ZSX Primus IV", manufactured by Rigaku Corporation), fluorescent X-ray analysis measurement was repeatedly performed five times using the following measurement conditions, the average value of each scan angle was calculated, and an X-ray spectrum was created. Furthermore, in the created X-ray spectrum, it was confirmed that a peak appeared near a scan angle of 28.2°, whereby it was confirmed that the light-transmissive conductive layer contained Kr atoms.

[0109] <Measurement conditions>

[0110] Spectrum: Kr-KA

[0111] Measurement diameter: 30 mm

[0112] Atmosphere: Vacuum

[0113] Target: Rh

[0114] Tube voltage: 50 kV

[0115] Tube current: 60 mA

[0116] Primary filter: Ni40

[0117] Scan angle (deg): 27.0 to 29.5

[0118] Step (deg): 0.020

[0119] Speed (deg / min): 0.75

[0120] Attenuator: 1 / 1

[0121] Slit: S2

[0122] Spectroscopic crystal: LiF (200)

[0123] Detector: SC

[0124] PHA: 100 to 300

[0125] [Table 1]

[0126]

[0127] Industrial applicability

[0128] The transparent conductive film produced by the present application can be used as a supply material for a conductor film for pattern formation of a transparent electrode for various devices such as liquid crystal displays, touch panels, and light sensors.

[0129] Explanation of reference signs

[0130] X Transparent conductive film

[0131] D Thickness direction

[0132] 10 Transparent substrate

[0133] 11 Transparent resin film

[0134] 12 Functional layer

[0135] 20 Light-transmissive conductive layer

[0136] 21 First region

[0137] 22 Second region

Claims

1. A method for producing a transparent conductive film, comprising: a preparation step of preparing a transparent substrate; and a film formation step of forming an amorphous light-transmissive conductive layer having a resistivity of 4.5 x 10 -4 Ω·cm or more and 12 x 10 -4 Ω·cm or less on the transparent substrate by a sputtering method, in the sputtering method of the film formation step, a sputtering gas containing a rare gas having an atomic number larger than argon and a reactive gas are used, and the light-transmissive conductive material is formed under conditions where the proportion of the reactive gas is 15% or less by flow rate and the film formation gas pressure is 0.04 Pa or more and 0.9 Pa or less.

2. The method for producing a transparent conductive film according to claim 1, wherein The rare gas is krypton and / or xenon.

3. The method for producing a transparent conductive film according to claim 1, wherein The proportion of krypton in the sputtering gas is 50% or more by volume.

4. The method for producing a transparent conductive film according to claim 1, wherein The light-transmissive conductive layer has a specific resistance of 2.2 x 10 -4 Ω·cm or less after a heat treatment at 155°C for 1 hour.

5. The method of producing a transparent conductive film according to claim 1, further comprising: a step of heating the light-transmissive conductive layer to crystallize it.

6. The method for producing a transparent conductive film according to any one of claims 1 to 5, further comprising: a step of patterning the light-transmissive conductive layer.

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