Transparent conductive layer and transparent conductive film

Abstract

To provide a transparent conductive layer and a transparent conductive film excellent in etching property.SOLUTION: The transparent conductive layer contains a rare gas having an atomic number larger than that of argon. A full width at half maximum of a peak in a (440) plane when the transparent conductive layer is subjected to X-ray diffraction is 0.27 degrees or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a transparent conductive layer and a transparent conductive film. [Background technology]

[0002] Transparent conductive films on organic polymer film substrates are known (see, for example, Patent Document 1 below). The transparent conductive film described in Patent Document 1 has low specific resistance. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-157814 Summary of the Invention [Problem to be solved by the invention]

[0004] Depending on the application and purpose, the transparent conductive film is patterned by etching.

[0005] Therefore, the transparent conductive film is sometimes required to have excellent etching properties.

[0006] The etching property is evaluated, for example, by the dissolution time. The dissolution time is the time it takes for the transparent conductive film to be removed per unit thickness of the transparent conductive film when one surface of the transparent conductive film in the thickness direction comes into contact with an etching solution and is dissolved and removed. The unit of the dissolution time is (seconds / nm). The shorter the dissolution time, the better the etching property.

[0007] However, the transparent conductive film described in Patent Document 1 has the drawback of not being able to satisfy the above requirements.

[0008] The present invention provides a transparent conductive layer and a transparent conductive film that are excellent in etching properties. [Means for solving the problem]

[0009] The present invention (1) is a transparent conductive layer comprising an inorganic oxide containing a rare gas having an atomic number greater than that of argon, and the transparent conductive layer has a half-width of a peak in a (440) plane of 0.27 degrees or less when subjected to X-ray diffraction.

[0010] The present invention (2) includes the transparent conductive layer according to (1), in which the inorganic oxide is an indium tin composite oxide.

[0011] The present invention (3) includes a transparent conductive film comprising a substrate and the transparent conductive layer according to (1) or (2) in this order toward one side in the thickness direction.

[0012] The present invention (4) includes the transparent conductive film according to (3), in which the substrate contains a resin.

[0013] The present invention (5) includes the transparent conductive film according to (3) or (4), in which the substrate is a resin. [Effects of the Invention]

[0014] The transparent conductive layer and transparent conductive film of the present invention have excellent etching properties. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is a cross-sectional view of one embodiment of a transparent conductive layer of the present invention. [Figure 2] FIG. 2 is a cross-sectional view of a transparent conductive film having the transparent conductive layer shown in FIG. [Figure 3] 1 is a graph showing the relationship between the amount of oxygen introduced and the resistivity in reactive sputtering in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0016] 1. One embodiment of the transparent conductive layer A transparent conductive layer 1 according to one embodiment of the present invention will be described with reference to Fig. 1. This transparent conductive layer 1 extends in a planar direction, which is perpendicular to the thickness direction. The transparent conductive layer 1 is crystalline.

[0017] 1.1 Inorganic oxides contained in the transparent conductive layer The transparent conductive layer 1 contains an inorganic oxide. Examples of inorganic oxides include metal oxides. The metal oxide contains at least one metal selected from the group consisting of In, Sn, Zn, Ga, Sb, Nb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. Specifically, preferred materials for the transparent conductive layer 1 include indium zinc composite oxide (IZO), indium gallium zinc composite oxide (IGZO), indium gallium composite oxide (IGO), indium tin composite oxide (ITO), and antimony tin composite oxide (ATO), and preferably indium tin composite oxide (ITO) is used from the viewpoint of improving etching properties.

[0018] 1.2 Tin oxide (SnO2) content The content of tin oxide (SnO2) in the indium tin composite oxide is, for example, 0.5 mass% or more, preferably 3 mass% or more, more preferably 6 mass% or more, and even more preferably 8 mass% or more, and is, for example, less than 50 mass%, preferably 25 mass% or less, and more preferably 15 mass% or less. When the content of tin oxide in the indium tin composite oxide is equal to or greater than the above-mentioned lower limit, excellent etching properties are obtained. When the content of tin oxide (SnO2) in the indium tin composite oxide is equal to or less than the above-mentioned upper limit, it is easy to achieve both excellent resistance properties and etching properties of the transparent conductive layer 1.

[0019] 1.3 Noble gases with atomic numbers greater than argon contained in inorganic oxides The inorganic oxide contains a rare gas 2 having an atomic number greater than that of argon. As shown in the enlarged upper view of FIG. 1, the rare gas 2 having an atomic number greater than that of argon is present throughout the entire transparent conductive layer 1 in the thickness direction.

[0020] The transparent conductive layer 1 is a composition in which an inorganic oxide (preferably a metal oxide) is mixed with a rare gas having an atomic number greater than that of argon.

[0021] Examples of rare gases with atomic numbers greater than that of argon include krypton, xenon, and radon. These can be used alone or in combination. Preferred rare gases with atomic numbers greater than that of argon include krypton and xenon, and more preferred is krypton (Kr) from the viewpoints of low cost and excellent electrical conductivity.

[0022] The method for identifying the rare gas with an atomic number greater than that of argon is not limited. For example, the rare gas with an atomic number greater than that of argon in the transparent conductive layer 1 can be identified (presence or absence can be determined) by Rutherford backscattering spectrometry, secondary ion mass spectrometry, laser resonance ionization mass spectrometry, and / or X-ray fluorescence analysis. However, from the viewpoint of analytical simplicity, the rare gas is preferably identified by X-ray fluorescence analysis. Details of X-ray fluorescence analysis are described in the Examples. When Rutherford backscattering spectrometry is performed to quantify the rare gas with an atomic number greater than that of argon, quantification is not possible because the content of the rare gas with an atomic number greater than that of argon is not equal to or greater than the detection limit (lower limit). However, when X-ray fluorescence analysis is performed and the presence of the rare gas with an atomic number greater than that of argon is identified, it is determined that the transparent conductive layer 1 includes a region in which the content of the rare gas with an atomic number greater than that of argon is 0.0001 atom% or greater.

[0023] The content of the rare gas having an atomic number higher than that of argon in the inorganic oxide (transparent conductive layer 1) is, for example, 0.0001 atom% or more, preferably 0.001 atom% or more, and for example, 1.0 atom% or less, more preferably 0.7 atom% or less, even more preferably 0.5 atom% or less, particularly preferably 0.3 atom% or less, particularly preferably 0.2 atom% or less, and most preferably 0.15 atom% or less. If the content of the rare gas having an atomic number higher than that of argon in the inorganic oxide (transparent conductive layer 1) is within the above range, the etching properties of the transparent conductive layer 1 can be improved.

[0024] Alternatively, a rare gas 2 having an atomic number larger than that of argon is present (distributed) in a portion of the transparent conductive layer 1 in the thickness direction, as shown in the enlarged view at the bottom of Fig. 1. In the embodiment shown in the enlarged view at the bottom of Fig. 1, the transparent conductive layer 1 has a first region 3 and a second region 4 in this order toward one side in the thickness direction.

[0025] The first region 3 contains a rare gas 2 having an atomic number greater than that of argon. The first region 3 may contain argon. Preferably, the first region 3 does not contain argon. The thickness ratio of the first region 3 to the transparent conductive layer 1 is, for example, 0.95 or less, preferably 0.8 or less, more preferably 0.7 or less, even more preferably 0.6 or less, and particularly preferably 0.48 or less, and also, for example, 0.01 or more, preferably 0.1 or more, and more preferably 0.3 or more. The thickness of the first region 3 is, for example, 5 nm or more, preferably 10 nm or more, more preferably 20 nm or more, even more preferably 30 nm or more, particularly preferably more than 40 nm, and particularly preferably 50 nm or more, and, for example, less than 300 nm, preferably 250 nm or less, more preferably 150 nm or less, even more preferably 100 nm or less, and particularly preferably 70 nm or less.

[0026] The content of the rare gas having an atomic number greater than that of argon in the first region 3 is, for example, 0.0001 atom% or more, preferably 0.001 atom% or more, and for example, 1.0 atom% or less, more preferably 0.7 atom% or less, even more preferably 0.5 atom% or less, particularly preferably 0.3 atom% or less, particularly preferably 0.2 atom% or less, and most preferably 0.15 atom% or less. If the content of the rare gas having an atomic number larger than that of argon in the first region 3 is within the above range, the etching properties of the first region 3 can be improved.

[0027] The second region 4 does not contain a noble gas 2 having an atomic number greater than that of argon. Alternatively, the second region 4 may contain, for example, argon or no argon. Preferably, the second region 4 does not contain a noble gas 2 having an atomic number greater than that of argon, but contains argon. The presence of argon is confirmed, for example, by performing Rutherford backscattering analysis. The ratio of the thickness of the second region 4 to the thickness of the first region 3 is, for example, 0.99 or more, preferably 0.9 or more, preferably 1.2 or more, and for example, 2.0 or less, preferably 1.5 or less. The thickness of the second region 4 is, for example, 5 nm or more, preferably 10 nm or more, more preferably 20 nm or more, even more preferably 30 nm or more, particularly preferably more than 40 nm, and particularly preferably 50 nm or more, and is, for example, less than 300 nm, preferably 250 nm or less, more preferably 200 nm or less, even more preferably 150 nm or less, particularly preferably 100 nm or less, particularly preferably 75 nm or less, and most preferably 70 nm or less.

[0028] In the sputtering process described below, if the sputtering gas contains argon, a large amount of argon is incorporated into the transparent conductive layer 1. In contrast, in this embodiment, in which the sputtering gas contains a rare gas with an atomic number greater than that of argon but does not contain argon, the transparent conductive layer 1 (or the first region 3) contains a rare gas with an atomic number greater than that of argon. In other words, the type of rare gas contained in the transparent conductive layer 1 differs between regions. The gas contained in the transparent conductive layer 1 acts as an impurity element and affects the crystal orientation of the transparent conductive layer 1 depending on the type of impurity element and the atomic size. This effect is particularly significant in this embodiment in which the base material 6 contains a resin. In this application, the transparent conductive layer 1 (or the first region 3) contains a rare gas with an atomic number greater than that of argon, thereby enabling favorable control of the orientation in the (440) plane, and as a result, the etching ability of the transparent conductive layer 1 (including the first region 3) is improved.

[0029] 1.4 X-ray diffraction peak on the (440) plane There is a peak in the (440) plane when X-ray diffraction is performed on the transparent conductive layer 1. The (440) plane is a specific peak included in the spectrum obtained when X-ray diffraction is performed on the crystalline transparent conductive layer 1.

[0030] 1.4.1 Half-width of the peak on the (440) plane The half-width of the peak in the (440) plane in X-ray diffraction is 0.27 degrees or less.

[0031] On the other hand, if the half-width of the peak in the (440) plane in X-ray diffraction exceeds 0.27 degrees, the etching properties of the transparent conductive layer 1 are poor.

[0032] In contrast, when the transparent conductive layer 1 is subjected to X-ray diffraction, the half width of the peak in the (440) plane is 0.27 degrees or less, and therefore the transparent conductive layer 1 has excellent etching properties.

[0033] When the transparent conductive layer 1 is subjected to X-ray diffraction, the half-width of the peak in the (440) plane is preferably 0.26 degrees or less, more preferably 0.25 degrees or less, even more preferably 0.24 degrees or less, particularly preferably 0.23 degrees or less, and most preferably 0.22 degrees or less.

[0034] Furthermore, when the transparent conductive layer 1 is subjected to X-ray diffraction, the half width of the peak in the (440) plane is, for example, 0.01 degrees or more, preferably 0.05 degrees or more, more preferably 0.10 degrees or more, and even more preferably 0.15 degrees or more.

[0035] If the half-width of the peak in the (440) plane is equal to or greater than the above-mentioned lower limit, side etching of the transparent conductive layer 1 due to excessive solubility can be suppressed. Side etching is a phenomenon in which the transparent conductive layer 1 is excessively removed when the transparent conductive layer 1 is shaped into a pattern by etching. Specifically, when a patterned etching resist is formed on one surface of the transparent conductive layer 1 in the thickness direction, and the transparent conductive layer 1 exposed from the pattern comes into contact with an etching solution, the etching solution removes the transparent conductive layer 1 toward the other side, and the transparent conductive layer 1 in contact with the edge of the etching resist is also excessively removed. In this case, when projected in the thickness direction, in the transparent conductive layer 1 overlapping the edge of the etching resist, one surface and its vicinity are largely removed toward the inside of the surface direction of the etching resist, while the other surface and its vicinity are largely removed toward the inside of the surface direction of the etching resist, or are barely removed at all.

[0036] There are no particular limitations on the method for adjusting the half-width of the peak in the (440) plane in X-ray diffraction to fall within the above range.

[0037] The half-width of the peak in the (440) plane of X-ray diffraction is measured based on the description in the Examples below.

[0038] 1.5 Dissolution time of transparent conductive layer 1 The dissolution time when the transparent conductive layer 1 is immersed in 7 mass % hydrochloric acid is, for example, 20 seconds / nm or less, preferably 18 seconds / nm or less, more preferably 17 seconds / nm or less, and even more preferably 16 seconds / nm or less, and is, for example, 1 second / nm or more. A short dissolution time means excellent etching properties. The measurement of the dissolution time will be described in the Examples below.

[0039] 1.6 Other physical properties of the transparent conductive layer 1 The crystal grain size in the transparent conductive layer 1 is, for example, 0.05 μm or more, preferably 0.1 μm or more, more preferably 0.15 μm or more, and for example, 3 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, even more preferably less than 0.4 μm, even more preferably 0.3 μm or less, and particularly preferably 0.25 μm or less. When the crystal grain size is equal to or greater than the above-mentioned lower limit, excellent etching properties are achieved. When the crystal grain size is equal to or less than the above-mentioned upper limit, cracks are less likely to occur in the transparent conductive layer 1, even when a substrate 6 containing a flexible resin is used. The crystal grain size can be determined, for example, by FE-SEM observation. Details of how to determine the crystal grain size are described in the Examples section below.

[0040] The transparent conductive layer 1 has a thickness of, for example, 15 nm or more, preferably 35 nm or more, more preferably 50 nm or more, even more preferably 75 nm or more, particularly preferably 100 nm or more, and particularly preferably 120 nm or more. The transparent conductive layer 1 has a thickness of, for example, 500 nm or less, preferably 300 nm or less, more preferably 250 nm or less, more preferably 200 nm or less, even more preferably 150 nm or less, particularly preferably 140 nm or less, and particularly preferably 135 nm or less.

[0041] The transparent conductive layer 1 has a total light transmittance of, for example, 75% or more, preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. There is no upper limit to the total light transmittance of the transparent conductive layer 1. The upper limit to the total light transmittance of the transparent conductive layer 1 is, for example, 100%.

[0042] The resistivity of the transparent conductive layer 1 is, for example, 5.0×10 -4 Ω·cm or less, preferably 3×10 -4 Ω cm or less, and for example, 0.1×10 -4 Ω·cm or more, preferably 1.1×10 -4 Resistivity is measured by the four-terminal method.

[0043] 1.7 Transparent conductive film5 Next, a transparent conductive film 5 including the above-described transparent conductive layer 1 will be described with reference to FIG. 2. The transparent conductive film 5 extends in the planar direction. The transparent conductive film 5 includes a substrate 6 and a transparent conductive layer 1, which are arranged in this order toward one side in the thickness direction. That is, in this embodiment, the transparent conductive film 5 includes the substrate 6 and the transparent conductive layer 1, which are arranged in this order toward one side in the thickness direction. In this embodiment, the transparent conductive film 5 includes only the substrate 6 and the transparent conductive layer 1.

[0044] 1.8 Base material 6 In this embodiment, the substrate 6 forms the other surface of the transparent conductive film 5 in the thickness direction. The substrate 6 improves the mechanical strength of the transparent conductive film 5. The substrate 6 extends in the planar direction. The substrate 6 contains, for example, a resin. If the substrate 6 contains a resin, it is possible to achieve both excellent resistance characteristics and etching properties in the transparent conductive layer 1. Preferably, the substrate 6 is made of a resin. If the substrate 6 is made of a resin, it is possible to achieve a transparent conductive film 5 that is flexible in addition to achieving both excellent resistance characteristics and etching properties in the transparent conductive layer 1. The resin will be described later. In this embodiment, the substrate 6 is not adjacent to a glass plate (not shown). In this embodiment, the other surface of the substrate 6 in the thickness direction does not contact the glass plate.

[0045] 1.8.1 Layer structure of substrate 6 In this embodiment, the substrate 6 includes a substrate sheet 61 and a functional layer 60 in this order in the thickness direction. In this embodiment, the functional layer 60 is a single layer. The functional layer 60 contacts one side of the substrate sheet 61 in the thickness direction. The functional layer 60 is preferably a hard coat layer 62. In this embodiment, the substrate 6 preferably includes a substrate sheet 61 and a hard coat layer 62 in this order toward the other side in the thickness direction.

[0046] 1.8.1.1 Base sheet 61 The base sheet 61 is flexible. Examples of the base sheet 61 include a resin film. The resin in the resin film is not limited. Examples of the resin include polyester resin, acrylic resin, olefin resin, polycarbonate resin, polyethersulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, polystyrene resin, and norbornene resin. From the viewpoints of transparency and mechanical strength, a polyester resin is preferably used as the resin. Examples of polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, and preferably PET.

[0047] The thickness of the base sheet 61 is preferably 1 μm or more, more preferably 10 μm or more, and even more preferably 30 μm or more. The thickness of the base sheet 61 is preferably 300 μm or less, more preferably 200 μm or less, even more preferably 150 μm or less, and particularly preferably 100 μm or less. The ratio of the thickness of the base sheet 61 to the thickness of the substrate 6 is, for example, 0% or more, preferably 50% or more, and even more preferably 80% or more, and for example, 99.99% or less, preferably 99% or less.

[0048] 1.8.1.2 Hard Coat Layer 62 The hard coat layer 62 makes one surface of the transparent conductive layer 1 in the thickness direction less susceptible to scratches. The hard coat layer 62 contacts one surface of the substrate sheet 61 in the thickness direction. The hard coat layer 62 is made of a resin. Specifically, the hard coat layer 62 is, for example, a cured layer of a curable composition containing a curable resin. Examples of the curable resin include acrylic resin, urethane resin, amide resin, silicone resin, epoxy resin, and melamine resin. Examples of the curable resin include acrylic resin. The thickness of the hard coat layer 62 is, for example, 0.1 μm or more, preferably 0.5 μm or more, and, for example, 10 μm or less, preferably 3 μm or less. The ratio of the thickness of the hard coat layer 62 to the thickness of the substrate sheet 61 is, for example, 0.1% or more, preferably 1% or more, and, for example, 100% or less, preferably 50% or less. The thickness of the hard coat layer 62 corresponds to the thickness of the functional layer 60.

[0049] 1.8.2 Thickness of substrate 6 The thickness of the substrate 6 is, for example, 5 μm or more, preferably 10 μm or more, more preferably 25 μm or more, and for example, 500 μm or less, preferably 200 μm or less, more preferably 100 μm or less. The thickness of the substrate 6 is the total thickness of the substrate sheet 61 and the hard coat layer 62.

[0050] 1.8.3 Physical properties of substrate 6 The total light transmittance of the substrate 6 is, for example, 75% or more, preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. The upper limit of the total light transmittance of the substrate 6 is not limited. The upper limit of the total light transmittance of the substrate 6 is, for example, 100%. The total light transmittance of the substrate 6 is determined based on JIS K 7375-2008. The total light transmittance of the following members is determined based on the same method as above.

[0051] The substrate 6 may be a commercially available product.

[0052] 1.9 Transparent conductive layer 1 In the transparent conductive film 5 of this embodiment, the transparent conductive layer 1 forms one surface of the transparent conductive film 5 in the thickness direction. The transparent conductive layer 1 is disposed on one surface of the substrate 6 in the thickness direction. The transparent conductive layer 1 contacts one surface of the substrate 6 in the thickness direction. In other words, the other surface of the transparent conductive layer 1 in the thickness direction contacts the substrate 6. In this embodiment, the other surface of the transparent conductive layer 1 contacts one surface of the hard coat layer 62 (functional layer 60) in the thickness direction.

[0053] As shown in the enlarged view at the bottom of FIG. 1, when the transparent conductive layer 1 has the first region 3 and the second region 4, the first region 3 is preferably disposed on one surface of the substrate 6 in the thickness direction. Preferably, the first region 3 contacts one surface of the hard coat layer 62 (see FIG. 2) in the thickness direction. As shown in the enlarged views at the bottom of FIG. 1 and FIG. 2, when the transparent conductive layer 1 has the first region 3 and the second region 4, the transparent conductive film 5 includes the substrate sheet 61, the hard coat layer 62, the first region 3, and the second region 4, in this order toward one side in the thickness direction. In other words, the second region 4 is disposed on the opposite side of the substrate 6 from the first region 3 in the thickness direction.

[0054] 1.10 Thickness and other physical properties of transparent conductive film 5 The transparent conductive film 5 has a thickness of, for example, 2 μm or more, preferably 20 μm or more, more preferably 30 μm or more, and for example, 300 μm or less, preferably 200 μm or less, more preferably 100 μm or less.

[0055] The transparent conductive film 5 has a total light transmittance of, for example, 75% or more, or preferably 80% or more, and for example, 100% or less.

[0056] 1.11 Manufacturing method of transparent conductive film 5 In this method, for example, each of the layers is laid down by a roll-to-roll process.

[0057] 1.11.1 Preparation of Substrate 6 First, the substrate 6 is prepared. Specifically, a curable composition is applied to one surface of a substrate sheet 61. Thereafter, the curable resin in the curable composition is cured by heat or ultraviolet irradiation. In this way, a hard coat layer 62 is formed on one surface of the substrate sheet 61. In this way, the substrate 6 is prepared.

[0058] 1.11.2 Formation of transparent conductive layer 1 Thereafter, the transparent conductive layer 1 is formed on one surface in the thickness direction of the substrate 6. Specifically, first, an amorphous transparent conductive layer is formed on one surface in the thickness direction of the substrate 6, and then the amorphous transparent conductive layer is converted to a crystalline material to form the transparent conductive layer 1.

[0059] 1.11.2.1 Formation of amorphous transparent conductive layer (sputtering process) The amorphous transparent conductive layer is formed by, for example, sputtering, preferably reactive sputtering.

[0060] In the sputtering, a sputtering apparatus is used, which includes a single film-forming roll and a single film-forming chamber.

[0061] The film formation chamber can supply a sputtering gas into the film formation chamber. The sputtering gas can be a rare gas having an atomic number greater than that of argon. Examples of rare gases having an atomic number greater than that of argon include krypton, xenon, and radon, and preferably krypton (Kr). The sputtering gas preferably does not contain argon.

[0062] The sputtering gas is preferably mixed with a reactive gas, such as oxygen. The ratio of the amount of reactive gas introduced to the total amount of sputtering gas and reactive gas introduced is, for example, 0.1% by flow or more, preferably 0.5% by flow or more, and, for example, less than 5.0% by flow, preferably 4.0% by flow or less, more preferably 3.5% by flow or less.

[0063] A single target is placed in a single film formation chamber. The target is, for example, a sintered body of the above-mentioned metal oxide.

[0064] As shown in the lower diagram of Figure 1, to provide the transparent conductive layer 1 with the first region 3 and the second region 4, a first sputtering step and a second sputtering step are carried out in this order. Specifically, a sputtering device is provided with first and second film formation chambers. The first and second film formation chambers are arranged in this order toward the downstream side in the transport direction of the substrate 6.

[0065] 1.11.2.2 First sputtering step In the first sputtering step, a first sputtering gas is introduced into the first film formation chamber. The first sputtering gas includes a rare gas having an atomic number greater than that of argon. Preferably, the first sputtering gas is a rare gas having an atomic number greater than that of argon. A first region 3 is formed by the first sputtering step.

[0066] 1.11.2.3 Second sputtering step In the second sputtering step, a second sputtering gas is introduced into the second film formation chamber. The second sputtering gas contains argon. Preferably, the second sputtering gas is argon. By the second sputtering step, a second region 4 is formed on one side of the first region 3.

[0067] The atmospheric pressure inside the sputtering apparatus is, for example, 1.0 Pa or less, and, for example, 0.01 Pa or more.

[0068] This produces a laminate including the substrate 6 and the amorphous transparent conductive layer. When the sputtering apparatus includes first and second film formation chambers, the amorphous transparent conductive layer includes the first region 3 and the second region 4.

[0069] 1.11.2.4 Conversion of amorphous transparent conductive layers to crystalline Thereafter, the amorphous transparent conductive layer is converted into a crystalline layer to form the transparent conductive layer 1 .

[0070] To convert the transparent conductive layer 1 into a crystalline layer, the amorphous transparent conductive layer (or the laminate including the amorphous transparent conductive layer) is heated.

[0071] The heating temperature is, for example, 80°C or higher, preferably 110°C or higher, more preferably 130°C or higher, and particularly preferably 150°C or higher, and for example, 200°C or lower, preferably 180°C or lower, more preferably 175°C or lower, and even more preferably 170°C or lower. The heating time is, for example, 1 minute or longer, preferably 3 minutes or longer, more preferably 5 minutes or longer, and for example, 5 hours or shorter, preferably 3 hours or shorter, and more preferably 2 hours or shorter. Heating is carried out, for example, in vacuum or in the atmosphere. From the viewpoint of obtaining excellent etching properties of the transparent conductive layer 1, heating is preferably carried out in the atmosphere.

[0072] Alternatively, the transparent conductive film 5 having an amorphous transparent conductive layer can be left in the atmosphere at a temperature in the range of 20°C or higher and lower than 80°C for, for example, 10 hours or longer, preferably 24 hours or longer, to convert the amorphous transparent conductive layer into a crystalline layer.

[0073] 1.12 Applications of Transparent Conductive Film5 The transparent conductive film 5 is used in, for example, articles. Examples of the articles include optical articles. More specifically, examples of the articles include touch sensors, electromagnetic wave shields, dimming elements, photoelectric conversion elements, heat ray control members, light-transmitting antenna members, light-transmitting heater members, image display devices, and lighting.

[0074] 2. Effects of one embodiment The transparent conductive layer 1 provided on the transparent conductive film 5 has excellent etching properties. In other words, the dissolution time of the transparent conductive layer 1 is short.

[0075] The transparent conductive layer 1 is etched and patterned depending on the type of article described above.

[0076] 3. Variations In the following modifications, the same components and steps as those in the above-described embodiment are denoted by the same reference numerals, and detailed descriptions thereof will be omitted. Furthermore, each modification can achieve the same effects as those in the above-described embodiment unless otherwise specified. Furthermore, the embodiment and modifications can be combined as appropriate.

[0077] In this modification, the transparent conductive film 5 includes a substrate 6, a second region 4, and a first region 3 in this order toward one side in the thickness direction.

[0078] In another variation, the transparent conductive layer 1 has a structure in which the first regions 3 and the second regions 4 are repeated.

[0079] In a modified example (not shown), the functional layer 60 is a multi-layer structure. The functional layer 60 is disposed on one side and the other side of the base sheet 61 in the thickness direction. For example, the functional layer 60 includes an optical adjustment layer and a hard coat layer. The optical adjustment layer is disposed on one side of the base sheet 61. The hard coat layer is disposed on the other side of the base sheet 61. [Example]

[0080] The present invention will be described in more detail below with reference to examples. Note that the present invention is not limited to these examples. Specific numerical values ​​of the blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be substituted with the upper limit (a numerical value defined as "equal to or less than") or lower limit (a numerical value defined as "equal to or more than" or "exceeding") of the corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the above "Modes for Carrying Out the Invention."

[0081] Example 1 A substrate 6 having a thickness of 52 μm was prepared.

[0082] Specifically, a substrate sheet 61 (50 μm thick, manufactured by Toray Industries, Inc.) made of PET was prepared. Next, a hard coat composition (ultraviolet-curable resin containing acrylic resin) was applied to one surface of the substrate sheet 61 in the thickness direction to form a coating film. Next, the coating film was cured by ultraviolet irradiation. As a result, a hard coat layer 62 having a thickness of 2 μm was formed on one surface of the substrate sheet 61. In this way, a substrate 6 was produced which was provided with the substrate sheet 61 and the hard coat layer 62 in this order toward one side in the thickness direction.

[0083] An amorphous transparent conductive layer was formed on one surface of the substrate 6 by reactive sputtering (execution of sputtering step). The conditions for reactive sputtering were as follows.

[0084] A sintered body of indium oxide and tin oxide was used as the target. The tin oxide concentration in the sintered body was 10 mass %. A voltage was applied to the target using a DC power supply. The horizontal magnetic field strength above the target was 90 mT. The ultimate vacuum in the film formation chamber of the DC magnetron sputtering device was 0.9 × 10 -4 The film formation chamber was evacuated to a vacuum until the pressure reached 0.2 Pa, and the substrate 6 was degassed. Thereafter, Kr as a sputtering gas and oxygen as a reactive gas were introduced into the film formation chamber, and the pressure in the film formation chamber was set to 0.2 Pa. The ratio of the amount of oxygen introduced to the total amount of Kr and oxygen introduced into the film formation chamber was approximately 2.5 flow %. As shown in FIG. 3, the amount of oxygen introduced was within region X of the resistivity-oxygen introduction amount curve, and the resistivity of the amorphous krypton-containing transparent conductive layer was 6.6×10 -4 The resistivity versus oxygen introduction amount curve shown in Figure 3 was created by investigating in advance the dependence of the resistivity of an amorphous krypton-containing transparent conductive layer on the amount of oxygen introduced when the layer was formed by reactive sputtering under the same conditions as above, except for the amount of oxygen introduced.

[0085] Thereafter, the laminate was heated in a hot air oven at 160° C. This converted the amorphous transparent conductive layer into a crystalline one, forming a transparent conductive layer 1. The thickness of the transparent conductive layer 1 was 130 nm.

[0086] In this way, a transparent conductive film 5 was produced which was provided with the substrate 6 and the amorphous transparent conductive layer in this order towards one side in the thickness direction.

[0087] <Example 2> A transparent conductive film was produced in the same manner as in Example 1. However, in forming the amorphous transparent conductive layer, the following changes were made, and the first sputtering step and the second sputtering step were carried out in this order.

[0088] The first sputtering step was carried out in the same manner as in Example 1. However, the amount of oxygen introduced was adjusted so that the resistivity of the amorphous krypton-containing transparent conductive layer was 6.5×10 -4 The pressure was changed to Ω·cm, and the ratio of the oxygen introduction amount to the total introduction amount of Kr and oxygen was changed to 2.6 flow %. An amorphous first region 3 was formed by the first sputtering step. The thickness of the first region 3 was 55 nm.

[0089] Subsequently, the second sputtering step was carried out. At this time, the sputtering gas was changed to argon, the pressure in the sputtering film-forming apparatus was changed to 0.4 Pa, and the amount of oxygen introduced was adjusted so that the resistivity of the amorphous second region 4 became 6.5×10 -4 The pressure was changed to Ω·cm, and the ratio of the oxygen introduction amount to the total introduction amount of Ar and oxygen was changed to 1.5 flow rate%. An amorphous second region 4 was formed by the second sputtering process. The thickness of the second region 4 was 75 nm.

[0090] <Comparative Example 1> The first sputtering step and the second sputtering step were carried out in the same manner as in Example 2, and then a transparent conductive film 5 was produced, except for the following changes.

[0091] In the first sputtering step, the sputtering gas was changed to argon, and the pressure inside the sputtering film formation apparatus was changed to 0.4 Pa. The thickness of the first region 3 was 19 nm.

[0092] In the second sputtering step, the tin oxide concentration in the target was changed to 3 mass %. The thickness of the second region 4 was 3 nm.

[0093] <Comparative Example 2> The first sputtering step and the second sputtering step were carried out in the same manner as in Example 2, and then a transparent conductive film 5 was produced, except for the following changes.

[0094] In the first sputtering step, the tin oxide concentration in the sintered body was changed to 3 mass %. The amount of oxygen introduced was changed to a value at which the resistivity in the first region 3 became 6.6 × 10 -4 The pressure was changed to Ω·cm, and the ratio of the oxygen introduction amount to the total introduction amount of Kr and oxygen was changed to 2.5 flow%. The amorphous transparent conductive layer was crystallized by contacting it with a heating roll in a vacuum heating device. The heating temperature was 160°C, and the heating time was 0.1 hours. The thickness of the first region 3 was 11 nm.

[0095] In the second sputtering step, the sputtering gas was changed from Kr to argon, and the thickness of the second region 4 was 11 nm.

[0096] <Evaluation> The transparent conductive films 5 of the examples and comparative examples were evaluated for the following items.

[0097] <Thickness> The thickness of the transparent conductive layer 1 was measured by FE-TEM observation. Specifically, first, a sample for cross-sectional observation of the transparent conductive layer 1 was prepared by FIB microsampling. In the FIB microsampling method, an FIB device (trade name "FB2200", manufactured by Hitachi) was used, and the acceleration voltage was set to 10 kV. Next, the thickness of the transparent conductive layer 1 in the sample for cross-sectional observation was measured by FE-TEM observation. In the FE-TEM observation, an FE-TEM device (trade name "JEM-2800", manufactured by JEOL) was used, and the acceleration voltage was set to 200 kV.

[0098] Furthermore, in Example 2, Comparative Example 1, and Comparative Example 2, before forming the second region 4, a sample for cross-sectional observation was prepared from the first region 3, and the sample was observed by FE-TEM to calculate the thickness of the first region 3.

[0099] The thickness of the second region 4 was calculated by subtracting the thickness of the first region 3 from the thickness of the transparent conductive layer 1 .

[0100] <FWHM of X-ray diffraction peak on (440) plane> The X-ray diffraction peaks of the transparent conductive layer 1 were obtained by X-ray diffraction measurement using a horizontal X-ray diffractometer (trade name "SmartLab", manufactured by Rigaku Corporation) under the following measurement conditions. The results are shown in Table 1.

[0101] [Measurement conditions] Parallel beam optical configuration Light source: CuKα ray (wavelength: 1.54059Å) Output: 45kV, 200mA Entrance slit system: Soller slit 5.0° Entrance slit: 1.000 mm Receiving slit: 20.100 mm Receiving slit: Parallel slit analyzer (PSA) 0.114 deg. Detector: Multi-dimensional pixel detector Hypix-3000 Sample stage: A specimen in which glass was attached to the substrate 6 of a transparent conductive film 5 via an adhesive layer was placed on a sample plate (4-inch wafer sample plate). Scan axis: 2θ / θ (Out of Plane measurement) Step interval: 0.02° Measurement speed: 0.8° / min Measurement range: 10°~90°

[0102] The X-ray peak profile was obtained by subtracting the background from the substrate 6 (substrate 6 heated under the same conditions as the transparent conductive layer 1 in each example and comparative example). Then, using analysis software (software name "SmartLab Studio II"), an X-ray diffraction peak profile corresponding to the (440) plane was created so that 2θ was in the range of 49.8° to 51.8°, and the X-ray diffraction peak was fitted (peak shape: split-type Pearson VII function, background type: B-spline, fitting condition: automatic) to determine the full width at half maximum (FWHM, unit: °) of the X-ray diffraction peak in the (440) plane.

[0103] The following procedure is carried out in measuring the half-width of the peak in the (440) plane of the X-ray diffraction. [1] A baseline passing through the two tails of the peak in the (440) plane is drawn on the X-ray diffraction chart. [2] The intensity from the peak top to the baseline on the (440) plane is obtained as the peak intensity. [3] Identify the intensity at half the peak intensity on the (440) plane. [4] For the peak on the (440) plane, the 2θ (degrees) between the two points at half maximum is taken as the full width at half maximum (FWHM).

[0104] It is determined by (440) using an X-ray diffraction apparatus equipped with a program including the above-mentioned procedure.

[0105] <Crystal grain size> One surface of the transparent conductive layer 1 was observed with an FE-SEM (apparatus: Hitachi, SU8020) to determine the crystal grain size of the transparent conductive layer 1. Specifically, the transparent conductive layer 1 was fixed to a stand, and then surface FE-SEM observation (accelerating voltage: 0.8 kV, observed image: secondary electron image) was performed to photograph the transparent conductive layer 1 in a planar view. The magnification was adjusted so that the crystal grains could be clearly observed.

[0106] The captured images were then analyzed to determine the area of ​​each grain boundary region from the number of pixels present in that region, and the diameter of a circle with the same area as that region was calculated as the grain size (equivalent circle diameter). The results are shown in Table 1.

[0107] <Dissolution time (etching ability)> The dissolution time (seconds / nm) of the transparent conductive layer 1 was measured to evaluate the etching property of the transparent conductive layer 1. The results are shown in Table 1.

[0108] Specifically, the transparent conductive film 5 was subjected to a cycle consisting of the following first step, second step, and third step in that order, one or more times.

[0109] If the etching was determined to be complete in the third step, the cycle was terminated. On the other hand, if the etching was determined to be incomplete in the third step, the cycle was repeated.

[0110] First step: The transparent conductive film 5 was immersed in hydrochloric acid with a concentration of 7% by mass. The immersion temperature was 35° C. The immersion time was 30 seconds. Second step: The transparent conductive film 5 was washed with water and then dried. Third step: On one surface (exposed surface) of the transparent conductive layer 1 of the transparent conductive film 5, the resistance between a pair of terminals spaced 15 mm apart (terminal-to-terminal resistance) was measured using a surface resistance measuring tester.

[0111] In the third step, if the measured inter-terminal resistance exceeded 100 kΩ or was not measurable, it was determined that dissolution (etching) of the transparent conductive layer 1 was completed in the first step of the cycle to which the third step belonged.

[0112] The dissolution time (more specifically, the dissolution time per unit thickness) was determined by dividing the cumulative immersion time (dissolution time) of multiple first steps by the thickness of the transparent conductive layer 1. A shorter dissolution time indicates better etching properties of the transparent conductive layer 1.

[0113] <Confirmation of Kr atoms in transparent conductive layer 1> The fact that the transparent conductive layers 1 in Examples 1 and 2 and Comparative Example 2 contained Kr atoms was confirmed as follows.

[0114] First, using a scanning X-ray fluorescence analyzer (trade name "ZSX PrimusIV", manufactured by Rigaku Corporation), X-ray fluorescence analysis measurement was 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 Kr atoms were contained in the transparent conductive layer 1.

[0115] [Measurement conditions] Spectrum; Kr-KA Measuring diameter: 30 mm 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

[0116] [Table 1] [Industrial Applicability]

[0117] Transparent conductive films are used in optical articles.

[0118] The above invention is provided as an exemplary embodiment of the present invention, but it is merely an example and should not be interpreted as being limiting. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the following claims. [Explanation of symbols]

[0119] 1. Transparent conductive layer 2. Noble Gases 5 Transparent conductive film 6 Base material

Claims

1. a transparent conductive layer containing an inorganic oxide containing a rare gas with an atomic number greater than that of argon; The transparent conductive layer, wherein when the transparent conductive layer is subjected to X-ray diffraction, the half-value width of the peak in the (440) plane is 0.27 degrees or less.

2. The transparent conductive layer according to claim 1 , wherein the inorganic oxide is an indium tin composite oxide.

3. A transparent conductive film comprising a substrate and the transparent conductive layer according to claim 1 or 2, arranged in this order toward one side in the thickness direction.

4. The transparent conductive film according to claim 3 , wherein the substrate comprises a resin.

5. The transparent conductive film according to claim 3 , wherein the substrate is a resin.

6. The transparent conductive film according to claim 4 , wherein the substrate is a resin.

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