Light-transmitting conductive films and transparent conductive films

Abstract

The present invention provides a light-transmitting conductive film suitable for reducing resistance and suppressing yellowing, a transparent conductive film equipped with the light-transmitting conductive film, and an article with the transparent conductive film. [Solution] The light-transmitting conductive film 20 contains an indium-containing conductive oxide and includes a first region 21 in at least a portion of its thickness that contains krypton in a content ratio of less than 0.1 atomic percent. The light-transmitting conductive film 20 also contains an indium-containing conductive oxide and includes a second region 22 in at least a portion of its thickness that does not contain krypton.

Description

[Technical Field]

[0001] This invention relates to a light-transmitting conductive film and a transparent conductive film. [Background technology]

[0002] Transparent electrodes in various devices such as liquid crystal displays, touch panels, and optical sensors are formed from a film that combines light transmittance and conductivity (a light-transmitting conductive film). This light-transmitting conductive film is also used as an antistatic layer in the device. The light-transmitting conductive film is formed, for example, by depositing a conductive oxide film on a transparent substrate using a sputtering method. In sputtering, an inert gas such as argon is used as the sputtering gas to collide with the target (the material supplied for film deposition) and eject atoms from the target surface. Regarding technologies related to such light-transmitting conductive films, see, for example, Patent Document 1 below. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 5-334924 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Light-transmitting conductive films are required to have low resistance. This requirement is particularly strong for light-transmitting conductive films used in transparent electrodes. Furthermore, for light-transmitting conductive films used in displays, windows, and automotive applications, it is also required that the yellowing be suppressed in order to ensure a good appearance.

[0005] The present invention provides a light-transmitting conductive film suitable for reducing resistance and suppressing yellowing, and a transparent conductive film equipped with the light-transmitting conductive film. [Means for solving the problem]

[0006] The present invention [1] includes a light-transmitting conductive film having thickness, wherein at least a portion of the thickness direction contains a region containing krypton in a content ratio of less than 0.1 atomic percent.

[0007] The present invention [2] includes the light-transmitting conductive film described in [1] above, which contains krypton in a content of less than 0.1 atomic percent throughout the entire thickness direction.

[0008] The present invention [3] includes the light-transmitting conductive film described in [1] above, wherein a region that does not contain krypton is included in at least a portion of the thickness direction.

[0009] The present invention [4] includes the light-transmitting conductive film described in [3] above, wherein the region that does not contain krypton contains argon.

[0010] The present invention [5] includes a patterned light-transmitting conductive film according to any one of [1] to [4] above.

[0011] The present invention [6] includes a transparent conductive film comprising a transparent substrate and a light-transmitting conductive film according to any one of [1] to [5] above, disposed on one side in the thickness direction of the transparent substrate. [Effects of the Invention]

[0012] The light-transmitting conductive film of the present invention contains a region containing krypton at a concentration of less than 0.1 atomic percent in at least a portion of its thickness, making it suitable for reducing resistance and suppressing yellowing. The transparent conductive film of the present invention, having such a light-transmitting conductive film, is suitable for reducing resistance and suppressing yellowing. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic cross-sectional view of one embodiment of the transparent conductive film of the present invention. [Figure 2] FIG. 1 schematically shows an example in which the light-transmissive conductive film of the transparent conductive film shown in FIG. 1 contains Kr in a partial region in the thickness direction. FIG. 2A shows a case where the light-transmissive conductive film includes a first region (Kr-containing region) and a second region (Kr-free region) in this order from the transparent substrate side. FIG. 2B shows a case where the light-transmissive conductive film includes a second region (Kr-free region) and a first region (Kr-containing region) in this order from the transparent substrate side. [Figure 3] FIG. 1 shows a manufacturing method of the transparent conductive film shown in FIG. 1. FIG. 3A shows a step of preparing a resin film, FIG. 3B shows a step of forming a functional layer on the resin film, FIG. 3C shows a step of forming a light-transmissive conductive film on the functional layer, and FIG. 3D shows a crystallization step of the light-transmissive conductive film. [Figure 4] FIG. 1 shows a case where the light-transmissive conductive film in the transparent conductive film shown in FIG. 1 is patterned. [Figure 5] It is a graph showing the relationship between the amount of oxygen introduced when forming the light-transmissive conductive film by the sputtering method and the specific resistance of the formed light-transmissive conductive film.

MODE FOR CARRYING OUT THE INVENTION

[0014] As shown in FIG. 1, the transparent conductive film X includes a transparent substrate 10 and a light-transmissive conductive film 20 in this order toward one side in the thickness direction D. The transparent conductive film X, the transparent substrate 10, and the light-transmissive conductive film 20 each have a shape that spreads in a direction (plane direction) orthogonal to the thickness direction D. The transmissive conductive film X and the light-transmissive conductive film 20 included therein are an element provided in a touch sensor, a light control element, a photoelectric conversion element, a heat ray control member, an antenna member, an electromagnetic wave shielding member, a heater member, a lighting device, an image display device, and the like.

[0015] The transparent substrate 10 includes a resin film 11 and a functional layer 12 in this order toward one side in the thickness direction D.

[0016] The resin film 11 is a flexible, transparent resin film. Examples of materials for the resin film 11 include polyester resin, polyolefin resin, acrylic resin, polycarbonate resin, polyethersulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, and polystyrene resin. Examples of polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of polyolefin resins include polyethylene, polypropylene, and cycloolefin polymers. Examples of acrylic resins include polymethacrylate. From the viewpoint of transparency and strength, for example, polyester resin is preferably used as the material for the resin film 11, and PET is more preferably used.

[0017] The surface of the resin film 11 facing the functional layer 12 may be surface modified. Examples of surface modification treatments include corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.

[0018] The thickness of the resin film 11 is preferably 1 μm or more, more preferably 10 μm or more, and even more preferably 30 μm or more. The thickness of the resin film 11 is preferably 300 μm or less, more preferably 200 μm or less, even more preferably 100 μm or less, and particularly preferably 75 μm or less. These configurations regarding the thickness of the resin film 11 are suitable for ensuring the handling of the transparent conductive film X.

[0019] The total light transmittance of the resin film 11 (JIS K 7375-2008) is preferably 60% or more, more preferably 80% or more, and even more preferably 85% or more. Such a configuration is suitable for ensuring the transparency required for the transparent conductive film X when it is provided in touch sensors, dimming elements, photoelectric conversion elements, heat control members, antenna members, electromagnetic wave shielding members, heater members, lighting devices, and image display devices, etc. The total light transmittance of the resin film 11 is, for example, 100% or less.

[0020] In this embodiment, the functional layer 12 is arranged on one surface of the resin film 11 in the thickness direction D. In this embodiment, the functional layer 12 is a hard coat layer that makes it difficult for scratches to form on the exposed surface (top surface in Figure 1) of the light-transmitting conductive film 20.

[0021] The hard coat layer is a cured product of a curable resin composition. Examples of resins contained in the curable resin composition include polyester resin, acrylic resin, urethane resin, amide resin, silicone resin, epoxy resin, and melamine resin. Examples of curable resin compositions include ultraviolet-curable resin compositions and thermosetting resin compositions. From the viewpoint of improving the manufacturing efficiency of the transparent conductive film X because it can be cured without high-temperature heating, an ultraviolet-curable resin composition is preferably used as the curable resin composition. Specifically, an example of an ultraviolet-curable resin composition is the hard coat layer forming composition described in Japanese Patent Application Publication No. 2016-179686.

[0022] The surface of the functional layer 12 facing the light-transmitting conductive film 20 may be surface-modified. Examples of surface modification treatments include corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.

[0023] 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. This configuration is suitable for achieving sufficient abrasion resistance in the light-transmitting conductive film 20. 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.

[0024] The thickness of the transparent substrate 10 is preferably 1 μm or more, more preferably 10 μm or more, even more 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, even more preferably 110 μm or less, and particularly preferably 80 μm or less. These configurations regarding the thickness of the transparent substrate 10 are suitable for ensuring the handling of the transparent conductive film X.

[0025] The total light transmittance (JIS K 7375-2008) of the transparent substrate 10 is preferably 60% or more, more preferably 80% or more, and even more preferably 85% or more. Such a configuration is suitable for ensuring the transparency required for the transparent conductive film X when it is provided in touch sensors, dimming elements, photoelectric conversion elements, heat control members, antenna members, electromagnetic wave shielding members, heater members, lighting devices, and image display devices. The total light transmittance of the transparent substrate 10 is, for example, 100% or less.

[0026] In this embodiment, the light-transmitting conductive film 20 is disposed on one surface of the transparent substrate 10 in the thickness direction D. The light-transmitting conductive film 20 is one embodiment of the light-transmitting conductive film of the present invention and possesses both light transmittance and conductivity. The light-transmitting conductive film 20 is a layer formed from a light-transmitting conductive material. The light-transmitting conductive material contains, for example, a conductive oxide as its main component.

[0027] Examples of conductive oxides include metal oxides containing at least one metal or metalloid selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. Specifically, examples of conductive oxides include indium-containing conductive oxides and antimony-containing conductive oxides. Examples of indium-containing conductive oxides include indium-tin composite oxide (ITO), indium-zinc composite oxide (IZO), indium-gallium composite oxide (IGO), and indium-gallium-zinc composite oxide (IGZO). An example of an antimony-containing conductive oxide is antimony-tin composite oxide (ATO). From the viewpoint of achieving high transparency and good electrical conductivity, indium-containing conductive oxides are preferably used as conductive oxides, and ITO is more preferably used. This ITO may contain metals or metalloids other than In and Sn in amounts less than the respective contents of In and Sn.

[0028] When ITO is used as the conductive oxide, the ratio of tin oxide content to the total content of indium oxide (In2O3) and tin oxide (SnO2) in the ITO is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more. The ratio of the number of tin atoms to the number of indium atoms in the ITO (number of tin atoms / number of indium atoms) is preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.03 or more, even more preferably 0.05 or more, and particularly preferably 0.07 or more. These configurations are suitable for ensuring the durability of the light-transmitting conductive film 20.

[0029] The ratio of tin oxide content to the total content of indium oxide (In2O3) and tin oxide (SnO2) in ITO is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 12% by mass or less. The ratio of the number of tin atoms to the number of indium atoms in ITO (number of tin atoms / number of indium atoms) is preferably 0.16 or less, more preferably 0.14 or less, and even more preferably 0.13 or less. These configurations are suitable for ensuring ease of crystallization by heating in the amorphous light-transmitting conductive film 20 formed in the film formation step of the transparent conductive film manufacturing method described later.

[0030] The ratio of tin atoms to indium atoms in ITO can be determined, for example, by identifying the relative abundance of indium and tin atoms in the sample being measured using X-ray photoelectron spectroscopy. The above-mentioned content of tin oxide in ITO can then be determined, for example, from the relative abundance of indium and tin atoms identified in this way. The above-mentioned content of tin oxide in ITO may also be determined from the tin oxide (SnO2) content of the ITO target used during sputter deposition.

[0031] The light-transmitting conductive film 20 contains krypton (Kr) as a noble gas atom. In this embodiment, the noble gas atom in the light-transmitting conductive film 20 originates from the noble gas atom used as a sputtering gas in the sputtering method described later for forming the light-transmitting conductive film 20. In this embodiment, the light-transmitting conductive film 20 is a film (sputtered film) formed by the sputtering method.

[0032] The light-transmitting conductive film 20 contains a Kr-containing region in a part of the thickness direction D in which the Kr content is less than 0.1 atomic%, preferably 0.09 atomic% or less, more preferably 0.08 atomic% or less, even more preferably 0.07 atomic% or less, even more preferably 0.06 atomic% or less, and particularly preferably 0.05 atomic% or less. The Kr content in this region is, for example, 0.0001 atomic% or more. Preferably, the light-transmitting conductive film 20 satisfies such a Kr content throughout the entire thickness direction D (in this case, the entire thickness direction D of the light-transmitting conductive film 20 is a Kr-containing region). Specifically, the Kr content in the light-transmitting conductive film 20 is less than 0.1 atomic%, preferably 0.09 atomic% or less, more preferably 0.08 atomic% or less, even more preferably 0.07 atomic% or less, even more preferably 0.06 atomic% or less, and particularly preferably 0.05 atomic% or less throughout the entire thickness direction D. These configurations are suitable for achieving good crystal growth and forming large crystal grains when the amorphous light-transmitting conductive film 20 is crystallized by heating during the manufacturing process of the transparent conductive film X, and therefore are suitable for obtaining a low-resistance light-transmitting conductive film 20 (the larger the crystal grains in the light-transmitting conductive film 20, the lower the resistance of the light-transmitting conductive film 20). Furthermore, the above configuration regarding the Kr content of the light-transmitting conductive film 20 is also suitable for suppressing the yellowing of the light-transmitting conductive film 20. In other words, the above configuration regarding the Kr content is suitable for achieving both low resistance and suppression of yellowing in the light-transmitting conductive film 20.

[0033] The Kr content of the light-transmitting conductive film 20 can be controlled by adjusting various conditions when the light-transmitting conductive film 20 is deposited by sputtering. These conditions include, for example, the Kr content of the sputtering gas introduced into the deposition chamber during sputtering, and the amount of sputtering gas introduced.

[0034] The presence and content of rare gas atoms such as Kr in the light-transmitting conductive film 20 are identified, for example, by Rutherford backscattering spectrometry, which will be described later with respect to the examples. The presence or absence of rare gas atoms such as Kr in the light-transmitting conductive film 20 is identified, for example, by X-ray fluorescence analysis, which will be described later with respect to the examples. In the light-transmitting conductive film under analysis, if the content of rare gas atoms cannot be quantified by Rutherford backscattering spectrometry because it is below the detection limit (lower limit), and the presence of rare gas atoms is identified by X-ray fluorescence analysis, then it is determined that the light-transmitting conductive film contains a region in which the content of rare gas atoms such as Kr is 0.0001 atomic percent or more.

[0035] The Kr content in the Kr-containing region of the light-transmitting conductive film 20 may be non-uniform in the thickness direction D. For example, in the thickness direction D, the Kr content may gradually increase or decrease as it moves away from the transparent substrate 10. Alternatively, in the thickness direction D, a portion of the film where the Kr content gradually increases as it moves away from the transparent substrate 10 may be located on the side of the transparent substrate 10, and a portion of the film where the Kr content gradually decreases as it moves away from the transparent substrate 10 may be located on the opposite side of the transparent substrate 10. Alternatively, in the thickness direction D, a portion of the film where the Kr content gradually decreases as it moves away from the transparent substrate 10 may be located on the side of the transparent substrate 10, and a portion of the film where the Kr content gradually increases as it moves away from the transparent substrate 10 may be located on the opposite side of the transparent substrate 10.

[0036] If the light-transmitting conductive film 20 contains noble gas atoms other than Kr, examples of noble gas atoms other than Kr include argon (Ar) and xenon (Xe). From the viewpoint of reducing the manufacturing cost of the transparent conductive film X, the light-transmitting conductive film 20 preferably does not contain Xe.

[0037] The content of noble gas atoms (including Kr) in the light-transmitting conductive film 20 is preferably 1.2 atomic% or less, more preferably 1.1 atomic% or less, even more preferably 1.0 atomic% or less, even more preferably 0.8 atomic% or less, even more preferably 0.5 atomic% or less, especially more preferably 0.4 atomic% or less, very preferably 0.3 atomic% or less, and particularly preferably 0.2 atomic% or less, throughout the entire thickness direction D. Such a configuration is suitable for achieving good crystal growth and forming large crystal grains when the amorphous light-transmitting conductive film 20 is crystallized by heating during the manufacturing process of the transparent conductive film X, and therefore is suitable for obtaining a low-resistance light-transmitting conductive film 20. The content of noble gas atoms in the light-transmitting conductive film 20 is preferably, for example, 0.0001 atomic% or more throughout the entire thickness direction D.

[0038] Figure 2 schematically illustrates an example where the light-transmitting conductive film 20 contains Kr in a portion of the thickness direction D. Figure 2A shows the case where the light-transmitting conductive film 20 contains a first region 21 and a second region 22 in that order from the transparent substrate 10 side. The first region 21 contains Kr. The second region 22 does not contain Kr, but contains, for example, a noble gas atom other than Kr. Figure 2B shows the case where the light-transmitting conductive film 20 contains a second region 22 and a first region 21 in that order from the transparent substrate 10 side. In Figure 2, the boundary between the first region 21 and the second region 22 is depicted by a dashed line, but in cases where the composition of the first region 21 and the second region 22 is not significantly different in aspects other than the trace amounts of noble gas atoms, the boundary between the first region 21 and the second region 22 may not be clearly distinguishable.

[0039] When the light-transmitting conductive film 20 includes a first region 21 (Kr-containing region) and a second region 22 (Kr-free region), from the viewpoint of suppressing the yellowing of the light-transmitting conductive film 20 and the transparent conductive film X, it is preferable that the light-transmitting conductive film 20 includes the first region 21 and the second region 22 in this order from the transparent substrate 10 side.

[0040] When the light-transmitting conductive film 20 includes a first region 21 and a second region 22, the ratio of the thickness of the first region 21 to the total thickness of the first region 21 and the second region 22 is, for example, 1% or more, preferably 20% or more, more preferably 30% or more, even more preferably 40% or more, and particularly preferably 50% or more. This ratio is less than 100%. Also, the ratio of the thickness of the second region 22 to the total thickness of the first region 21 and the second region 22 is, for example, 99% or less, preferably 80% or less, more preferably 70% or less, even more preferably 60% or less, and particularly preferably 50% or less. These configurations are preferred from the viewpoint of suppressing the yellowing of the light-transmitting conductive film 20 and the yellowing of the transparent conductive film X.

[0041] The thickness of the light-transmitting conductive film 20 is preferably 10 nm or more, more preferably 30 nm or more, even more preferably 50 nm or more, even more preferably 80 nm or more, and particularly preferably 100 nm or more. Such a configuration is suitable for reducing the resistance of the light-transmitting conductive film 20. Furthermore, the thickness of the light-transmitting conductive film 20 is, for example, 1000 nm or less, preferably less than 300 nm, more preferably less than 250 nm, even more preferably less than 200 nm, especially preferably less than 160 nm, particularly preferably less than 150 nm, and most preferably less than 148 nm. Such a configuration is suitable for reducing the compressive residual stress of the light-transmitting conductive film 20 and suppressing warping of the transparent conductive film X.

[0042] The total light transmittance (JIS K 7375-2008) of the light-transmitting conductive film 20 is preferably 60% or more, more preferably 80% or more, and even more preferably 85% or more. Such a configuration is suitable for ensuring transparency in the light-transmitting conductive film 20. Alternatively, the total light transmittance of the light-transmitting conductive film 20 may be, for example, 100% or less.

[0043] In this embodiment, the light-transmitting conductive film 20 is a crystalline film. The crystalline nature of the light-transmitting conductive film can be determined, for example, as follows: First, the light-transmitting conductive film (in the case of the transparent conductive film X, the light-transmitting conductive film 20 on the transparent substrate 10) is immersed in 5% by mass hydrochloric acid at 20°C for 15 minutes. Next, the light-transmitting conductive film is washed with water and then dried. Then, the resistance between a pair of terminals separated by 15 mm (inter-terminal resistance) is measured on the exposed plane of the light-transmitting conductive film (in the case of the transparent conductive film X, the surface of the light-transmitting conductive film 20 opposite to the transparent substrate 10). If the inter-terminal resistance is 10 kΩ or less in this measurement, the light-transmitting conductive film is a crystalline film. Furthermore, the crystalline nature of the light-transmitting conductive film can also be determined by observing the presence of crystal grains in the light-transmitting conductive film in a planar view using a transmission electron microscope.

[0044] The resistivity of the light-transmitting conductive film 20 (crystalline film) is preferably 2.2 × 10⁻⁶ -4 Ω·cm or less, more preferably 2 × 10⁻⁶ -4 Ω·cm or less, more preferably 1.9 × 10⁻⁶ -4 Ω·cm or less, particularly preferably 1.8 × 10⁻⁶ -4 The resistivity is Ω·cm or less. This configuration is suitable for ensuring the low resistance required for the light-transmitting conductive film 20 when the transparent conductive film X is provided in touch sensor devices, dimming elements, photoelectric conversion elements, heat control members, antenna members, heater members, electromagnetic wave shielding members, lighting devices, and image display devices. Furthermore, the resistivity of the light-transmitting conductive film 20 is preferably 0.1 × 10⁻⁶. -4 Ω·cm or more, more preferably 0.5 × 10 -4 Ω·cm or greater, more preferably 1.0 × 10⁻⁶ -4 It is greater than or equal to Ω·cm.

[0045] The resistivity of the light-transmitting conductive film 20 is determined by multiplying the surface resistance of the light-transmitting conductive film 20 by its thickness. The resistivity can be controlled, for example, by adjusting the Kr content in the light-transmitting conductive film 20 and by adjusting various conditions when the light-transmitting conductive film 20 is sputter-deposited. Examples of such conditions include the temperature of the substrate (transparent substrate 10 in this embodiment) on which the light-transmitting conductive film 20 is deposited, the amount of oxygen introduced into the deposition chamber, the atmospheric pressure in the deposition chamber, and the horizontal magnetic field strength on the target.

[0046] The transparent conductive film X is manufactured, for example, as follows:

[0047] First, prepare the resin film 11 as shown in Figure 3A.

[0048] Next, as shown in Figure 3B, a functional layer 12 is formed on one surface of the resin film 11 in the thickness direction D. By forming the functional layer 12 on the resin film 11, a transparent substrate 10 is produced.

[0049] The functional layer 12 described above, which serves 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 this coating film. If the curable resin composition contains an ultraviolet-curable resin, the coating film is cured by ultraviolet irradiation. If the curable resin composition contains a thermosetting resin, the coating film is cured by heating.

[0050] The exposed surface of the functional layer 12 formed on the resin film 11 is subjected to surface modification treatment as needed. When plasma treatment is used as the surface modification treatment, argon gas, for example, is used as the inert gas. The discharge power in the plasma treatment is, for example, 10W or more, and for example, 5000W or less.

[0051] Next, as shown in Figure 3C, an amorphous light-transmitting conductive film 20 is formed on the transparent substrate 10 (film formation process). Specifically, the material is deposited on the functional layer 12 of the transparent substrate 10 by sputtering to form an amorphous light-transmitting conductive film 20 (this light-transmitting conductive film 20 is converted into a crystalline light-transmitting conductive film 20 by heating in the crystallization process described later).

[0052] In the sputtering method, it is preferable to use a sputtering deposition apparatus that can perform the film deposition process in a roll-to-roll manner. When using a roll-to-roll sputtering deposition apparatus in the manufacture of a transparent conductive film X, a long transparent substrate 10 is moved from the feed roll to the winding roll of the apparatus, and a material is deposited on the transparent substrate 10 to form a light-transmitting conductive film 20. In this sputtering method, a sputtering deposition apparatus with one deposition chamber may be used, or a sputtering deposition apparatus with multiple deposition chambers arranged sequentially along the travel path of the transparent substrate 10 may be used (when forming a light-transmitting conductive film 20 including the first region 21 and the second region 22 described above, a sputtering deposition apparatus with two or more deposition chambers is used).

[0053] In the sputtering method, specifically, a sputtering gas (inert gas) is introduced into the deposition chamber of a sputtering deposition apparatus under vacuum conditions, while a negative voltage is applied to a target placed on the cathode in the deposition chamber. This generates a glow discharge, ionizing the gas atoms, which then collide with the target surface at high speed, ejecting the target material from the target surface. This ejected target material is then deposited onto the functional layer 12 of the transparent substrate 10.

[0054] As the target material placed on the cathode in the film deposition chamber, the conductive oxides described above are used for the light-transmitting conductive film 20, preferably indium-containing conductive oxides are used, and more preferably ITO is used. When ITO is used, the ratio of the tin oxide content to the total content of tin oxide and indium oxide in the ITO is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, even more preferably 5% by mass or more, particularly preferably 7% by mass or more, and also preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 12% by mass or less.

[0055] The sputtering method is preferably a reactive sputtering method. In the reactive sputtering method, a reactive gas is introduced into the deposition chamber in addition to the sputtering gas.

[0056] In the case of forming a light-transmitting conductive film 20 containing Kr over the entire thickness direction D (first case), the gas introduced into one or more deposition chambers of the sputtering deposition apparatus contains Kr as a sputtering gas and oxygen as a reactive gas. The sputtering gas may also contain inert gases other than Kr. Examples of inert gases other than Kr include noble gas atoms other than Kr. Examples of noble gas atoms include Ar and Xe. The Kr content in the gas introduced into the deposition chamber is preferably 50% by volume or more, more preferably 60% by volume or more, even more preferably 70% by volume or more, and also, for example, 100% by volume or less.

[0057] In the case of forming a light-transmitting conductive film 20 including the first region 21 and the second region 22 described above (the second case), the gas introduced into the deposition chamber for forming the first region 21 contains Kr as a sputtering gas and oxygen as a reactive gas. The sputtering gas may also contain an inert gas other than Kr. The type of inert gas other than Kr is the same as described above in the first case. The Kr content in the gas introduced into the deposition chamber is preferably 50% by volume or more, more preferably 60% by volume or more, even more preferably 70% by volume or more, and also, for example, 100% by volume or less.

[0058] Furthermore, in the second case described above, the gas introduced into the deposition chamber for forming the second region 22 contains an inert gas other than Kr as a sputtering gas and oxygen as a reactive gas. Examples of the inert gas other than Kr include the inert gases mentioned above as the inert gas other than Kr in the first case, and Ar is preferably used.

[0059] In reactive sputtering, the ratio of the amount of sputtering gas introduced to the total amount of sputtering gas and oxygen introduced into the deposition chamber is, for example, 85% or more and, for example, 99.99% or less. The ratio of the amount of oxygen introduced to the total amount of sputtering gas and oxygen introduced into the deposition chamber is, for example, 0.01% or more and, for example, 15% or less.

[0060] The atmospheric pressure inside the deposition chamber during film deposition by sputtering (sputter deposition) is, for example, 0.02 Pa or higher, and also, for example, 1 Pa or lower.

[0061] The temperature of the transparent substrate 10 during sputtering is, for example, 100°C or less, preferably 50°C or less, more preferably 30°C or less, even more preferably 10°C or less, and particularly preferably 0°C or less, and also, for example, -50°C or higher, preferably -20°C or higher, more preferably -10°C or higher, and even more preferably -7°C or higher.

[0062] Examples of power sources for applying voltage to the target include DC power supplies, AC power supplies, MF power supplies, and RF power supplies. A DC power supply and an RF power supply may be used in combination. The absolute value of the discharge voltage during sputter deposition is, for example, 50V or more, and also, for example, 500V or less. The horizontal magnetic field strength on the target surface is, for example, 10mT or more, preferably 60mT or more, and also, for example, 300mT or less. Such a configuration is preferable for suppressing an excess amount of krypton atoms in the light-transmitting conductive layer 20, and therefore is preferable for suppressing yellowness and reducing resistance in the formed light-transmitting conductive film 20.

[0063] In this manufacturing method, the light-transmitting conductive film 20 is then converted from amorphous to crystalline (crystallized) by heating, as shown in Figure 3D (crystallization step). Examples of heating methods include infrared heaters and ovens (heat transfer heating ovens, hot air heating ovens). The heating environment may be either a vacuum environment or an atmospheric environment. Preferably, heating is carried out in the presence of oxygen. 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, 10 hours or less, preferably 200 minutes or less, more preferably 90 minutes or less, and even more preferably 60 minutes or less, and also, for example, 1 minute or more, preferably 5 minutes or more.

[0064] In this manner, the transparent conductive film X is manufactured.

[0065] The light-transmitting conductive film 20 in the transparent conductive film X may be patterned, as schematically shown in Figure 4. The light-transmitting conductive film 20 can be patterned by etching it through a predetermined etching mask. The patterning of the light-transmitting conductive film 20 may be performed before or after the crystallization process described above. The patterned light-transmitting conductive film 20 can function, for example, as a wiring pattern.

[0066] The light-transmitting conductive film 20 of the transparent conductive film X contains a region containing krypton at a concentration of less than 0.1 atomic percent in at least a portion of its thickness, making it suitable for reducing resistance and suppressing yellowing. Because the transparent conductive film X is equipped with such a light-transmitting conductive film 20, it is suitable for reducing resistance and suppressing yellowing. Specifically, this is shown in the examples and comparative examples described below.

[0067] In the transparent conductive film X, the functional layer 12 may be an adhesion-enhancing layer to achieve high adhesion of the light-transmitting conductive film 20 to the transparent substrate 10. A configuration in which the functional layer 12 is an adhesion-enhancing layer is suitable for ensuring adhesion between the transparent substrate 10 and the light-transmitting conductive film 20.

[0068] The functional layer 12 may be an index-matching layer for adjusting the reflectivity of the surface (one side in the thickness direction D) of the transparent substrate 10. A configuration in which the functional layer 12 is an index-matching layer is suitable for making the pattern shape of the light-transmitting conductive film 20 on the transparent substrate 10 less visible when the light-transmitting conductive film 20 is patterned.

[0069] The functional layer 12 may be a release functional layer that makes it practically possible to peel the light-transmitting conductive film 20 from the transparent substrate 10. A configuration in which the functional layer 12 is a release functional layer is suitable for peeling the light-transmitting conductive film 20 from the transparent substrate 10 and transferring the light-transmitting conductive film 20 to another component.

[0070] The functional layer 12 may be a composite layer in which multiple layers are connected in the thickness direction D. Preferably, the composite layer includes two or more layers selected from the group consisting of a hard coat layer, an adhesion-enhancing layer, a refractive index-adjusting layer, and a release-functional layer. Such a configuration is suitable for the functional layer 12 to exhibit the above-mentioned functions of each selected layer in combination. In one preferred embodiment, the functional layer 12 comprises an adhesion-enhancing layer, a hard coat layer, and a refractive index-adjusting layer on the resin film 11 in this order toward one side in the thickness direction D. In another preferred embodiment, the functional layer 12 comprises a release-functional layer, a hard coat layer, and a refractive index-adjusting layer on the resin film 11 in this order toward one side in the thickness direction D.

[0071] The transparent conductive film X is used after being laminated to an article and, if necessary, patterned with a light-transmitting conductive film 20. The transparent conductive film X is laminated to the article, for example, via a bonding functional layer.

[0072] Examples of articles include elements, components, and devices. Specifically, examples of articles with a transparent conductive film include elements with a transparent conductive film, components with a transparent conductive film, and devices with a transparent conductive film.

[0073] Examples of elements include dimming elements and photoelectric conversion elements. Examples of dimming elements include current-driven dimming elements and electric field-driven dimming elements. Examples of current-driven dimming elements include electrochromic (EC) dimming elements. Examples of electric field-driven dimming elements include PDLC (polymer dispersed liquid crystal) dimming elements, PNLC (polymer network liquid crystal) dimming elements, and SPD (suspended particle device) dimming elements. Examples of photoelectric conversion elements include solar cells. Examples of solar cells include organic thin-film solar cells and dye-sensitized solar cells. Examples of components include electromagnetic wave shielding members, heat control members, heater members, and antenna members. Examples of devices include touch sensor devices, lighting devices, and image display devices.

[0074] Articles with a transparent conductive film are suitable for improving performance in functions that depend on the light transmittance and conductivity of the light-transmitting conductive film 20, because the light-transmitting conductive film 20 of the transparent conductive film X is suitable for reducing resistance. Furthermore, articles with a transparent conductive film are suitable for ensuring a good appearance because the light-transmitting conductive film 20 of the transparent conductive film X is suitable for suppressing yellowing.

[0075] Examples of the above-mentioned adhesive functional layer include an adhesive layer and a bonding layer. The material of the adhesive functional layer is not particularly limited as long as it is transparent and exhibits adhesive properties. Preferably, the adhesive functional layer is formed from a resin. Examples of resins include acrylic resin, silicone resin, polyester resin, polyurethane resin, polyamide resin, polyvinyl ether resin, vinyl acetate / vinyl chloride copolymer, modified polyolefin resin, epoxy resin, fluororesin, natural rubber, and synthetic rubber. Acrylic resin is preferred as the resin because it exhibits adhesive properties such as cohesiveness, adhesion, and appropriate wettability, has excellent transparency, and has excellent weather resistance and heat resistance.

[0076] The adhesive layer (the resin forming the adhesive layer) may contain a corrosion inhibitor to suppress corrosion of the light-transmitting conductive film 20. The adhesive layer (the resin forming the adhesive layer) may also contain a migration inhibitor (for example, a material disclosed in Japanese Patent Application Publication No. 2015-022397) to suppress migration of the light-transmitting conductive film 20. Furthermore, the adhesive layer (the resin forming the adhesive layer) may contain an ultraviolet absorber to suppress deterioration of the article when used outdoors. Examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxalic acid anilide compounds, cyanoacrylate compounds, and triazine compounds.

[0077] Furthermore, when the transparent substrate 10 of the transparent conductive film X is fixed to an article via a fixing functional layer, the light-transmitting conductive film 20 (including the light-transmitting conductive film 20 after patterning) is exposed on the transparent conductive film X. In such cases, a cover layer may be placed on the exposed surface of the light-transmitting conductive film 20. The cover layer is a layer that covers the light-transmitting conductive film 20, improving the reliability of the light-transmitting conductive film 20 and suppressing functional degradation due to damage to the light-transmitting conductive film 20. Such a cover layer is preferably formed from a dielectric material, and more preferably from a composite material of a resin and an inorganic material. Examples of resins include the resins described above for the fixing functional layer. Examples of inorganic materials include inorganic oxides and fluorides. Examples of inorganic oxides include silicon oxide, titanium oxide, niobium oxide, aluminum oxide, zirconium dioxide, and calcium oxide. Examples of fluorides include magnesium fluoride. Furthermore, the cover layer (a mixture of resin and inorganic materials) may contain the above-mentioned corrosion inhibitors, migration inhibitors, and ultraviolet absorbers. [Examples]

[0078] The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. Furthermore, the specific numerical values ​​such as the amounts (contents), physical properties, and parameters described below can be substituted with the upper limits (numerical values ​​defined as "less than or equal to" or "less than") or lower limits (numerical values ​​defined as "greater than or equal to" or "greater than") of the corresponding amounts (contents), physical properties, and parameters described in the "Modes for Carrying Out the Invention" above.

[0079] [Comparative Example 3] A long roll of PET film (50 μm thick, manufactured by Toray Industries, Inc.) was coated with an ultraviolet-curable resin containing acrylic resin to form a coating film. Next, the coating film was cured by ultraviolet irradiation to form a hard coat layer (2 μm thick). In this way, a transparent substrate comprising a resin film and a hard coat layer as a functional layer was fabricated.

[0080] Next, a 30 nm thick amorphous, light-transmitting conductive film was formed on the hard coat layer of a transparent substrate using reactive sputtering. For the reactive sputtering method, a sputtering apparatus (DC magnetron sputtering apparatus) capable of performing the film deposition process in a roll-to-roll manner was used. The sputtering deposition conditions in this embodiment were as follows:

[0081] A sintered body of indium oxide and tin oxide (tin oxide concentration 10 mass%) was used as the target. A DC power supply was used to apply voltage to the target (horizontal magnetic field strength on the target was 90 mT). The deposition temperature (temperature of the transparent substrate on which the light-transmitting conductive film was laminated) was set to -5°C. The ultimate vacuum level in the deposition chamber of the apparatus was 0.7 × 10⁻⁶. -4After evacuating the film formation chamber to a vacuum until reaching Pa, Kr as a sputtering gas and oxygen as a reactive gas were introduced into the film formation chamber, and the atmospheric pressure in the film formation chamber was set to 0.3 Pa. The ratio of the oxygen introduction amount to the total introduction amount of Kr and oxygen introduced into the film formation chamber was about 2.6 flow rate %, and the oxygen introduction amount was within the region R of the specific resistance-oxygen introduction amount curve as shown in FIG. 5, and the value of the specific resistance of the formed film was 6.4×10 -4 Ω·cm was adjusted. The specific resistance-oxygen introduction amount curve shown in FIG. 5 can be prepared in advance by examining the oxygen introduction amount dependence of the specific resistance of the optically transparent conductive film when the optically transparent conductive film is formed by reactive sputtering under the same conditions as above except for the oxygen introduction amount.

[0082] Next, the optically transparent conductive film on the transparent substrate was crystallized by heating in a hot air oven (crystallization step). In this step, the heating temperature was 165°C and the heating time was 1 hour.

[0083] In the above manner, the transparent conductive film of Comparative Example 3 was produced. The optically transparent conductive film (thickness 30 nm, crystalline) of the transparent conductive film of Comparative Example 3 consists of a single Kr-containing ITO layer.

[0084] 〔Example 2〕 The transparent conductive film of Example 2 was produced in the same manner as the transparent conductive film of Comparative Example 3, except for the following.

[0085] In the formation of the optically transparent conductive film, a first sputter film formation for forming a first region (thickness 28 nm) of the optically transparent conductive film on the transparent substrate and a second sputter film formation for forming a second region (thickness 102 nm) of the optically transparent conductive film on the first region were sequentially performed.

[0086] The conditions for the first sputtering deposition in this embodiment are as follows: A sintered body of indium oxide and tin oxide (tin oxide concentration of 10 mass%) was used as the target. A DC power supply was used to apply voltage to the target (horizontal magnetic field strength on the target was 90 mT). The deposition temperature was -5°C. The ultimate vacuum level in the first deposition chamber of the apparatus was set to 0.7 × 10⁻⁶. -4 After setting the pressure to Pa, Kr as a sputtering gas and oxygen as a reactive gas were introduced into the deposition chamber, and the atmospheric pressure inside the deposition chamber was set to 0.2 Pa. The amount of oxygen introduced into the deposition chamber was such that the resistivity of the formed film was 6.4 × 10⁻⁶. -4 It was adjusted to be Ω·cm.

[0087] The conditions for the second sputter deposition in this embodiment are as follows: The ultimate vacuum level in the second deposition chamber of the apparatus is set to 0.7 × 10⁻⁶ -4 After setting the pressure to Pa, Ar as the sputtering gas and oxygen as the reactive gas were introduced into the deposition chamber, and the atmospheric pressure inside the deposition chamber was set to 0.4 Pa. In this embodiment, the other conditions for the second sputter deposition were the same as those for the first sputter deposition.

[0088] The transparent conductive film of Example 2 was fabricated as described above. The light-transmitting conductive film (thickness 130 nm, crystalline) of the transparent conductive film of Example 2 has, in order from the transparent substrate side, a first region (thickness 28 nm) consisting of a Kr-containing ITO layer and a second region (thickness 102 nm) consisting of an Ar-containing ITO layer.

[0089] [Comparative Example 4] The transparent conductive film of Comparative Example 4 was prepared in the same manner as the transparent conductive film of Comparative Example 3, except for the following in the sputtering deposition process: A mixed gas of krypton and argon (Kr 90 vol%, Ar 10 vol%) was used as the sputtering gas. The atmospheric pressure in the deposition chamber was set to 0.2 Pa.

[0090] The light-transmitting conductive film (30 nm thick, crystalline) of the transparent conductive film in Comparative Example 4 consists of a single ITO layer containing Kr and Ar.

[0091] [Comparative Example 1] The transparent conductive film of Comparative Example 1 was prepared in the same manner as the transparent conductive film of Comparative Example 3, except for the following:

[0092] In sputter deposition, Ar was used as the sputtering gas, and a light-transmitting conductive film with a thickness of 130 nm was deposited.

[0093] The light-transmitting conductive film (130 nm thick) of the transparent conductive film in Comparative Example 2 consists of a single Ar-containing ITO layer.

[0094] [Comparative Example 2] A light-transmitting conductive film was formed in the same manner as in Comparative Example 3, except that Ar was used as the sputtering gas during sputtering deposition. The light-transmitting conductive film (30 nm thick) of the transparent conductive film in Comparative Example 2 consisted of a single Ar-containing ITO layer.

[0095] <Thickness of light-transmitting conductive film> The thickness of each light-transmitting conductive film in Example 2 and Comparative Examples 1-4 was measured by FE-TEM observation. Specifically, first, samples for cross-sectional observation of each light-transmitting conductive film in Example 2 and Comparative Examples 1-4 were prepared by the FIB microsampling method. For the FIB microsampling method, a FIB device (product name "FB2200", manufactured by Hitachi) was used, and the acceleration voltage was set to 10kV. Next, the thickness of the light-transmitting conductive film in the cross-sectional observation samples was measured by FE-TEM observation. For the FE-TEM observation, a FE-TEM device (product name "JEM-2800", manufactured by JEOL) was used, and the acceleration voltage was set to 200kV.

[0096] In Example 2, the thickness of the first region of the light-transmitting conductive film was measured by FE-TEM observation of a sample prepared from an intermediate fabrication before the formation of the second region on the first region. In Example 2, the thickness of the second region of the light-transmitting conductive film was determined by subtracting the thickness of the first region from the total thickness of the light-transmitting conductive film in Example 2.

[0097] <Specific resistance> The resistivity of the light-transmitting conductive film in each transparent conductive film in Example 2 and Comparative Examples 1-4 was investigated. Specifically, first, the surface resistance of the light-transmitting conductive film in the transparent conductive film was measured using the four-terminal method in accordance with JIS K 7194 (1994). Then, the resistivity (Ω·cm) was determined by multiplying the surface resistance value by the thickness of the light-transmitting conductive film. The results are shown in Table 1.

[0098] <Evaluation of yellowness> The yellow tint of the light-transmitting conductive film in each transparent conductive film in Example 2 and Comparative Examples 1-4 was investigated. Specifically, the transmitted color of the transparent conductive film was measured using an integrating sphere spectroscopic transmittance analyzer (device name "DOT-3C", manufactured by Murakami Color Technology Laboratory). * a * b * b in the color system * (b) * A smaller value indicates a less yellowish hue. For this measurement, a D65 light source was used. The results of this measurement are shown in Table 1.

[0099] <Quantitative analysis of noble gas atoms in light-transmitting conductive films> The Kr and Ar atom content in each light-transmitting conductive film in Example 2 and Comparative Examples 1-4 was analyzed by Rutherford backscatter spectroscopy (RBS). For the five elements detected—In+Sn (since RBS makes it difficult to separate In and Sn, they were evaluated as a sum of the two elements), O, Ar, and Kr—the elemental ratios were determined to determine the abundance (atomic %) of Kr and Ar atoms in the light-transmitting conductive films. The equipment and measurement conditions used are as follows. The analysis results, including Kr content (atomic %) and Ar content (atomic %), are shown in Table 1. Regarding the analysis of Kr content, in Comparative Examples 3 and 4, reliable measurements above the detection limit (lower limit) could not be obtained (the detection limit varies depending on the thickness of the light-transmitting conductive film being measured; for the thickness of the light-transmitting conductive film in Comparative Example 3, the detection limit is 0.10 atomic %). Therefore, in Table 1, the Kr content of the light-transmitting conductive film is indicated as "< 0.10" to show that it is below the detection limit.

[0100] In Example 2, to determine the Kr atom content, a sample for Kr content measurement was prepared from an intermediate material before the formation of the second region on the first region of the light-transmitting conductive film, and the Kr content was determined in the same manner as in Comparative Examples 3 and 4. However, as in Comparative Examples 3 and 4, it was below the detection limit, so it is written as "< 0.10" to indicate that it is less than the detection limit (0.10) at the thickness of the light-transmitting conductive film in the first region. Furthermore, the Ar atom content was determined using a light-transmitting conductive film (thickness 130 nm) consisting of a laminate of the first and second regions as a sample, in the same manner as in Comparative Examples 1 to 4.

[0101] <Equipment used> Pelletron 3SDH (manufactured by National Electrostatics Corporation) <Measurement conditions> Incident ions: 4 He ++ Incident energy: 2300 keV Incident angle: 0deg Scattering angle: 160deg Sample current: 6nA Beam diameter: 2mmφ In-plane rotation: None Irradiation dose: 75μC

[0102] <Confirmation of Kr atoms in a light-transmitting conductive film> The presence of Kr atoms in each light-transmitting conductive film in Example 2 and Comparative Examples 3 and 4 was confirmed as follows. First, using a scanning X-ray fluorescence analyzer (product name "ZSX PrimusIV", manufactured by Rigaku Corporation), X-ray fluorescence analysis measurements were repeated five times under the following measurement conditions, and the average value for each scanning angle was calculated to create an X-ray spectrum. Then, by confirming that a peak appeared near a scanning angle of 28.2° in the created X-ray spectrum, it was confirmed that the light-transmitting conductive film contained Kr atoms.

[0103] <Measurement conditions> Spectrum; Kr-KA Measurement diameter: 30mm Atmosphere: Vacuum Target: Rh Tube voltage: 50kV Tube current: 60mA Primary filter: Ni40 Scanning angle (deg): 27.0~29.5 Step (deg): 0.020 Speed ​​(deg / min): 0.75 Attenuator: 1 / 1 Slit: S2 Spectroscopic crystal: LiF(200) Detector: SC PHA: 100-300

[0104] [Table 1]

[0105] [evaluation] In Example 2 and Comparative Examples 3 and 4, the transparent conductive films contain Kr in the light-transmitting conductive film. The resistivity of such light-transmitting conductive films is lower than that of the light-transmitting conductive films (without Kr) in Comparative Examples 1 and 2.

[0106] In addition, in each of the transparent conductive films in Example 2 and Comparative Examples 3 and 4, the Kr content of the light-transmitting conductive film is less than 0.1 atomic percent. In transparent conductive films equipped with such light-transmitting conductive films, b is lower than in each of the transparent conductive films in Comparative Examples 1 and 2. * The value is small, and therefore the yellow tint is suppressed. Specifically, it is as follows:

[0107] In the transparent conductive films of Example 2 and Comparative Examples 1-4, the transparent color b * The value depends on the thickness of the light-transmitting conductive film in each film (b of the transmitted color of the transparent substrate). * (The value is the same for all transparent conductive films). Comparing the transparent conductive films of Comparative Examples 3 and 4, which have the same thickness of light-transmitting conductive film, with the transparent conductive film of Comparative Example 2, the transparent conductive films of Comparative Examples 3 and 4 have a higher b value than the transparent conductive film of Comparative Example 2. * The value of is small, and the yellowing is suppressed. In other words, the light-transmitting conductive films in Comparative Examples 3 and 4 have less yellowing than the light-transmitting conductive film in Comparative Example 2. Also, comparing the transparent conductive film of Example 2 and the transparent conductive film of Comparative Example 1, which have the same thickness of light-transmitting conductive film, the transparent conductive film of Example 2 has a lower b value than the transparent conductive film of Comparative Example 1. * The value is small, and the yellow tint is suppressed. In other words, the light-transmitting conductive film in Example 2 has a more suppressed yellow tint than the light-transmitting conductive film in Comparative Example 1. [Industrial applicability]

[0108] The light-transmitting conductive film of the present invention can be used, for example, as a conductive film for patterning transparent electrodes in various devices such as liquid crystal displays, touch panels, and optical sensors. The transparent conductive film of the present invention can be used as a supply material for such conductive films. [Explanation of symbols]

[0109] X Transparent conductive film D thickness direction 10 Transparent base material 11 Resin film 12 Functional Layers 20 Light-transparent conductive film

Claims

1. A light-transmitting conductive film having thickness, A first region containing an indium-containing conductive oxide and containing krypton in a content of less than 0.1 atomic percent is included in at least a portion of the thickness direction. A light-transmitting conductive film comprising an indium-containing conductive oxide and a second region that does not contain krypton, comprising at least a portion of the thickness direction.

2. The light-transmitting conductive film according to claim 1, wherein the second region contains argon.

3. A light-transmitting conductive film according to claim 1 or 2, which is patterned.

4. Transparent substrate and A transparent conductive film comprising a light-transmitting conductive film according to any one of claims 1 to 3, disposed on one side in the thickness direction of the transparent substrate.

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