Conductive film and conductive film manufacturing method

Abstract

A conductive film (1) is provided with: an organic resin substrate (2); an inorganic layer (3) disposed on one side in the thickness direction of the organic resin base material (2); and a copper layer (4) disposed directly on one surface in the thickness direction of the inorganic layer (3). Y calculated according to a specified relational expression is less than 23.200.

Description

Technical Field

[0001] The present invention relates to a conductive film and a method for manufacturing the conductive film. Background Art

[0002] Conventionally, there is known a conductive film including a substrate and a metal layer in this order. Such a conductive film is used as a conductor layer for patterning electrodes in various devices such as flat panel displays and touch panels.

[0003] Such a conductive film is produced by, for example, disposing a metal layer on one surface in the thickness direction of a substrate by a sputtering method.

[0004] On the other hand, in the production of the above-mentioned conductive film, outgassing from the substrate sometimes occurs. Due to such outgassing, metal oxides are formed on the other side of the thickness direction of the metal layer. As a result, there is a disadvantage that the adhesion between the substrate and the metal layer is reduced.

[0005] In view of this, a conductive film having a barrier layer (rust-proof layer) between the substrate and the metal layer has been studied. The barrier layer can block outgassing from the substrate, thereby eliminating the above-mentioned inconvenience.

[0006] As such a conductive film, a conductive film including a resin film, a rust-proof layer, and a copper layer in this order has been proposed (for example, refer to Patent Document 1).

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2017-100368 Summary of the invention

[0010] Problems to be solved by the invention

[0011] On the other hand, if a barrier layer is provided, there is an undesirable condition that the specific resistance of the metal layer becomes higher. Specifically, in the case where the metal layer is a copper layer, if a barrier layer is provided, the crystal growth of the (200) plane of the copper layer in the out-of-plane diffraction measurement of the X-ray diffraction method is hindered. In this way, the crystal grains become smaller, and the crystal interface that hinders the movement of electrons increases. As a result, there is an undesirable condition that the specific resistance becomes higher.

[0012] The present invention provides a conductive film having an inorganic layer for blocking outgassing from an organic resin substrate and having a low specific resistance, and a method for producing the conductive film.

[0013] Solutions for solving problems

[0014] The present invention [1] is a conductive film comprising: an organic resin substrate; an inorganic layer disposed on one side in the thickness direction of the organic resin substrate; and a copper layer disposed directly on one side in the thickness direction of the inorganic layer, wherein Y calculated according to the following formula (1) is less than 23.200.

[0015] Y=-0.0002243×(α 111 / t)+5.764×β 111 -0.02178×γ 111 -0.02283×(α 200 / t)

[0016] -0.009098×γ 200 +0.01051×t+28.15……(1)

[0017] (In the above formula (1), α 111 β represents the integrated intensity of the peak of the (111) plane of the copper layer in the out-of-plane diffraction measurement of the X-ray diffraction method. t represents the thickness of the copper layer (nm). 111 It represents the integrated intensity ratio of the integrated intensity of the peak of the (111) plane of the copper layer to the integrated intensity of all the peaks of the copper layer in the out-of-plane diffraction measurement of the X-ray diffraction method. 111 This shows the crystallite size of the (111) plane of the copper layer in the out-of-plane diffraction measurement by the X-ray diffraction method. α 200 It represents the integrated intensity of the peak of the (200) plane of the copper layer in the out-of-plane diffraction measurement by the X-ray diffraction method. 200 This shows the crystallite size of the (200) plane of the copper layer in the out-of-plane diffraction measurement by the X-ray diffraction method. )

[0018] The present invention [2] includes the conductive film according to the above [1], wherein the copper layer has a thickness of 50 nm or more.

[0019] The present invention [3] includes the conductive film according to [1] or [2] above, wherein the copper layer has a thickness of 300 nm or less.

[0020] The present invention [4] includes the conductive film according to any one of [1] to [3] above, wherein the thickness of the inorganic layer is 2 nm or more and 15 nm or less.

[0021] The present invention [5] is a method for manufacturing a conductive film, which comprises: a first step of preparing an organic resin substrate; a second step of configuring an inorganic layer on one surface of the organic resin substrate in the thickness direction by sputtering; and a third step of configuring a copper layer on one surface of the inorganic layer in the thickness direction by sputtering, wherein in at least one of the second step and the third step, an inert gas is supplied as a sputtering gas, and oxygen is supplied.

[0022] The present invention [6] includes a method for manufacturing a conductive film as described in [5] above, wherein in the second step, an inert gas is supplied as a sputtering gas, and oxygen is supplied, and the flow rate of the oxygen in the second step is greater than 5 sccm and less than 200 sccm.

[0023] The present invention [7] includes a method for manufacturing a conductive film as described in [5] above, wherein in the third step, an inert gas and oxygen are supplied as sputtering gas, and the third step includes: a step 3A, in which an inert gas and oxygen are supplied by sputtering to configure a first copper layer on one surface in the thickness direction of the inorganic layer; and a step 3B, in which an inert gas is supplied without supplying oxygen to configure a second copper layer on one surface in the thickness direction of the first copper layer by sputtering, and the flow rate of oxygen in the step 3A is greater than 1 sccm and less than 20 sccm.

[0024] The present invention [8] includes a method for manufacturing a conductive film as described in [5] above, wherein in the second step and the third step, an inert gas and oxygen are supplied as sputtering gases, and the third step includes: a step 3A, in which an inert gas and oxygen are supplied by sputtering to configure a first copper layer on one surface in the thickness direction of the inorganic layer; and a step 3B, in which an inert gas is supplied without oxygen and a second copper layer is disposed on one surface in the thickness direction of the first copper layer by sputtering, wherein the flow rate of oxygen in the second step is greater than 10 sccm and less than 200 sccm, and the flow rate of oxygen in the step 3A is less than the flow rate of oxygen in the second step and is greater than 1 sccm and less than 20 sccm.

[0025] Effects of the Invention

[0026] The conductive film of the present invention includes an inorganic layer. Therefore, when the conductive film is produced, outgassing from the organic resin substrate can be blocked. As a result, a decrease in adhesion between the organic resin substrate (inorganic layer) and the copper layer can be suppressed.

[0027] In addition, Y calculated from a predetermined relational expression of the conductive film is less than 23.200. Therefore, the specific resistance of the copper layer can be reduced.

[0028] In the method for producing a conductive film of the present invention, in at least one of the second step and the third step, an inert gas is supplied as a sputtering gas and oxygen is supplied, so that a conductive film having a copper layer with low specific resistance can be produced. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 One embodiment of the conductive film of the present invention is shown.

[0030] Figure 2A to Figure 2C One embodiment of a method for producing a conductive film is shown. Figure 2A This shows the first step of preparing an organic resin substrate. Figure 2B This shows the second step of disposing an inorganic layer on one surface in the thickness direction of the organic resin substrate. Figure 2C This shows the third step of disposing a copper layer on one surface in the thickness direction of the inorganic layer.

[0031] Figure 3A to Figure 3D One embodiment of a method for producing a conductive film is shown. Figure 3A This shows the first step of preparing an organic resin substrate. Figure 3B This shows the second step of disposing an inorganic layer on one surface in the thickness direction of the organic resin substrate. Figure 3C The 3A step of disposing the first copper layer on one surface in the thickness direction of the inorganic layer is shown. Figure 3D The 3B step of disposing the second copper layer on one surface in the thickness direction of the first copper layer is shown. DETAILED DESCRIPTION

[0032] Reference Figure 1 , one embodiment of the conductive film of the present invention is described.

[0033] exist Figure 1 In the figure, the up-down direction on the paper is the up-down direction (thickness direction). In addition, the upper side on the paper is the upper side (one side in the thickness direction). In addition, the lower side on the paper is the lower side (the other side in the thickness direction). In addition, the left-right direction on the paper and the depth direction are the surface directions orthogonal to the up-down direction. Specifically, according to the direction arrows in each figure.

[0034] The conductive film 1 has a film shape (including a sheet shape) having a predetermined thickness. The conductive film 1 extends in a plane direction perpendicular to the thickness direction. The conductive film 1 has a flat upper surface and a flat lower surface.

[0035] like Figure 1As shown, the conductive film 1 comprises: an organic resin substrate 2; an inorganic layer 3, which is arranged on one side in the thickness direction of the organic resin substrate 2; and a copper layer 4, which is directly arranged on one surface in the thickness direction of the inorganic layer 3. Specifically, the conductive film 1 comprises: an organic resin substrate 2; an inorganic layer 3, which is directly arranged on the upper surface (one side in the thickness direction) of the organic resin substrate 2; and a copper layer 4, which is directly arranged on the upper surface (one surface in the thickness direction) of the inorganic layer 3.

[0036] The thickness of the conductive film 1 is, for example, 300 μm or less, or preferably 200 μm or less, and, for example, 1 μm or more, or preferably 5 μm or more.

[0037] <Organic resin base material>

[0038] The organic resin substrate 2 has a film shape. The organic resin substrate 2 has flexibility. The organic resin substrate 2 is disposed on the entire lower surface of the inorganic layer 3 so as to be in contact with the lower surface of the inorganic layer 3. The organic resin substrate 2 is the lowermost layer of the conductive film 1.

[0039] As the organic resin substrate 2, for example, a polymer film can be mentioned.

[0040] Examples of materials for polymer films include polyester resins, (meth) acrylic resins, olefin resins, polycarbonate resins, polyethersulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, and polystyrene resins. Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of (meth) acrylic resins include polymethyl methacrylate. Examples of olefin resins include polyethylene, polypropylene, and cycloolefin polymers. Examples of cellulose resins include cellulose triacetate.

[0041] As a material for the polymer film, preferably, polyester resin is used, and as a material for the polymer film, more preferably, polyethylene terephthalate is used.

[0042] The thickness of the organic resin substrate 2 is, for example, 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more, and, for example, 200 μm or less, preferably 150 μm or less, more preferably 100 μm or less.

[0043] The thickness of the organic resin substrate 2 can be measured using a micrometer (“DG-205” manufactured by PEACOCK).

[0044] Furthermore, the organic resin substrate 2 preferably has transparency. Specifically, the total light transmittance (JIS K 7375-2008) of the organic resin substrate 2 is, for example, 80% or more, or preferably 85% or more.

[0045] <Inorganic layer>

[0046] The inorganic layer 3 is a layer for shielding outgassing from the organic resin substrate 2 in the method for producing the conductive film 1 described later.

[0047] The inorganic layer 3 has a film shape and is disposed on the entire upper surface of the organic resin substrate 2 so as to be in contact with the upper surface of the organic resin substrate 2. The inorganic layer 3 is disposed on the entire lower surface of the copper layer 4 so as to be in contact with the lower surface of the copper layer 4.

[0048] Although the details will be described later, the inorganic layer 3 is formed by a sputtering method and is therefore a sputtered layer.

[0049] The material of the inorganic layer 3 is not particularly limited as long as it is an inorganic substance other than copper. Specifically, preferred examples of the material of the inorganic layer 3 include metals (excluding copper) and metal oxides (excluding copper oxide).

[0050] Examples of the metal include Ni, In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Pd, W, alloys thereof, and alloys thereof with copper. Preferably, CuNi is used as the metal.

[0051] Examples of the metal oxide include oxides of the above-mentioned metals. Preferred examples of the metal oxide include oxides containing indium. Examples of the indium-containing oxide include indium tin composite oxide (ITO).

[0052] Furthermore, the metal oxide may be either crystalline or amorphous.

[0053] As a material of the inorganic layer 3, metal oxides are preferably used.

[0054] The material of the inorganic layer 3 may be used alone or in combination of two or more.

[0055] For example, from the viewpoint of gas barrier properties, the thickness of the inorganic layer 3 is 2 nm or more. Also, for example, from the viewpoint of processability, the thickness of the inorganic layer 3 is 15 nm or less, preferably 10 nm or less, and more preferably 7 nm or less.

[0056] In addition, the thickness of the inorganic layer 3 can be measured by observing the cross section of the conductive film 1 using a transmission electron microscope, for example.

[0057] <Copper layer>

[0058] The copper layer 4 is a conductor layer and is formed into a desired pattern as required.

[0059] The copper layer 4 has a film shape and is disposed on the entire upper surface of the inorganic layer 3 so as to be in contact with the upper surface of the inorganic layer 3. The copper layer 4 is the uppermost layer of the conductive film 1.

[0060] Although the details will be described later, the copper layer 4 is formed by a sputtering method and is therefore a sputtered layer.

[0061] Examples of the material of the copper layer 4 include copper and copper alloys.

[0062] The metal constituting the copper alloy is not particularly limited, and examples thereof include silver, tin, chromium, and zirconium.

[0063] As a material of the copper layer 4, copper is preferably used from the viewpoint of electrical conductivity. That is, the copper layer 4 is preferably composed of copper.

[0064] The specific resistance of the copper layer 4 is, for example, 2.300×10 －8 Ω·m or less, preferably 2.200×10 －8 Ω·m or less, more preferably 2.150×10 －8 Ω·m or less, more preferably 2.100×10 －8 Ω·m or less, particularly preferably 2.050×10 －8 Ω·m or less, and usually 1.000×10 －8 Ω·m or more.

[0065] In addition, the specific resistance can be calculated by multiplying the surface resistance value measured by the four-probe method in accordance with JIS K7194 by the thickness of the copper layer 4 .

[0066] The surface resistance value of the copper layer 4 is, for example, 0.2200 Ω / □ or less, preferably 0.2000 Ω / □ or less, and more preferably 0.1500 Ω / □ or less.

[0067] The lower limit of the surface resistance value of the copper layer 4 is not particularly limited. For example, the surface resistance value of the copper layer 4 is usually greater than 0Ω / □.

[0068] In addition, the surface resistance value can be measured by a four-terminal method in accordance with JIS K7194.

[0069] For example, from the viewpoint of resistance value, the thickness of the copper layer 4 is 50 nm or more, preferably 70 nm or more, more preferably 90 nm or more, and further preferably 100 nm or more. Furthermore, for example, from the viewpoint of productivity, the thickness of the copper layer 4 is 300 nm or less, preferably 250 nm or less, more preferably 210 nm or less, further preferably 200 nm or less, particularly preferably 150 nm or less, and most preferably 120 nm or less.

[0070] It should be noted that the thickness of the copper layer 4 can be measured using, for example, cross-sectional TEM analysis.

[0071] <Method for producing conductive film>

[0072] Reference Figure 2A to Figure 2C as well as Figure 3A to Figure 3D , a method for manufacturing the conductive film 1 is described.

[0073] The method for manufacturing the conductive film 1 includes: a first step of preparing an organic resin substrate 2; a second step of disposing an inorganic layer 3 on one surface in the thickness direction of the organic resin substrate 2 by sputtering; and a third step of disposing a copper layer 4 on one surface in the thickness direction of the inorganic layer 3 by sputtering. In this method, each layer is sequentially disposed, for example, by a roll-to-roll method. In such a case, the conveying speed is, for example, 1.0 m / min or more, and, for example, 20.0 m / min or less.

[0074] In the method for manufacturing the conductive film 1, sputtering is performed while supplying a sputtering gas in the second and third steps, but in at least one of the second and third steps, an inert gas (described later) is supplied as a sputtering gas, and oxygen is supplied.

[0075] That is, in the method for manufacturing the conductive film 1, in the second step, an inert gas and oxygen are supplied by sputtering to arrange the inorganic layer 3 on one surface in the thickness direction of the organic resin substrate 2, and / or in the third step, an inert gas and oxygen are supplied by sputtering to arrange the copper layer 4 on one surface in the thickness direction of the inorganic layer 3. Thus, the formula (1) described later is satisfied.

[0076] In the following description, a first method of supplying oxygen in the second step and not supplying oxygen in the third step; a second method of not supplying oxygen in the second step and supplying oxygen in the third step; and a third method of supplying oxygen in both the second step and the third step are described in detail.

[0077] [First method]

[0078] In the first method, oxygen is supplied in the second step, and oxygen is not supplied in the third step.

[0079] (First process)

[0080] In the first step, Figure 2A As shown, an organic resin substrate 2 is prepared.

[0081] (Second process)

[0082] In the second step, Figure 2BAs shown, the inorganic layer 3 is disposed on one surface in the thickness direction of the organic resin substrate 2 by sputtering.

[0083] When the inorganic layer 3 is disposed on one surface in the thickness direction of the organic resin substrate 2 by sputtering, first, the one surface in the thickness direction of the organic resin substrate 2 is subjected to a surface treatment as necessary.

[0084] Examples of the surface treatment include corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow treatment, and saponification treatment.

[0085] Next, in the sputtering method, a target (material of the inorganic layer 3) and an organic resin substrate 2 are placed opposite each other in a vacuum chamber in a sputtering film forming device. Then, a sputtering gas is supplied and a voltage is applied from a power supply to accelerate gas ions, irradiate the target, and eject the target material from the target surface. Then, the target material is deposited on the surface (one side in the thickness direction) of the organic resin substrate 2 to form an inorganic layer 3.

[0086] In addition, as sputtering gas, an inert gas (eg, argon gas) and oxygen gas are supplied.

[0087] The flow rate of oxygen gas is, for example, 5 sccm or more, preferably 30 sccm or more, more preferably 60 sccm or more, further preferably 80 sccm or more, particularly preferably 120 sccm or more, and, for example, is 200 sccm or less.

[0088] Furthermore, the flow rate ratio of the flow rate of the inert gas to the flow rate of the oxygen gas is, for example, 3.5 or more, and for example, 200 or less.

[0089] The gas pressure during sputtering is, for example, 0.1 Pa or more, preferably 0.2 Pa or more, and, for example, 2.0 Pa or less.

[0090] The power source may be, for example, any of a DC power source, an AC power source, an MF power source, and an RF power source, or a combination thereof.

[0091] The discharge output is, for example, 1.0 kW or more, preferably 10.0 kW or more, and, for example, 20 kW or less.

[0092] Thus, the inorganic layer 3 is disposed on one surface in the thickness direction of the organic resin substrate 2 .

[0093] (Third process)

[0094] In the third step, Figure 2C As shown, the copper layer 4 is disposed on one surface in the thickness direction of the inorganic layer 3 by sputtering.

[0095] In the sputtering method, a target (material of the copper layer 4) and an inorganic layer 3 are arranged opposite to each other in a vacuum chamber of a sputtering film forming device. Then, a sputtering gas is supplied and a voltage is applied from a power supply to accelerate gas ions, irradiate the target, and eject the target material from the target surface. Then, the target material is deposited on the surface (one side in the thickness direction) of the inorganic layer 3 to form a copper layer 4.

[0096] In addition, an inert gas was supplied as the sputtering gas, and oxygen gas was not supplied.

[0097] The gas pressure during sputtering is, for example, 0.1 Pa or more, preferably 0.2 Pa or more, and, for example, 2.0 Pa or less.

[0098] The power source may be, for example, any of a DC power source, an AC power source, an MF power source, and an RF power source, or a combination thereof.

[0099] The discharge output is, for example, 10 kW or more, preferably 50 kW or more, and, for example, 150 kW or less.

[0100] The film formation temperature (the temperature of the organic resin substrate 2 on which the inorganic layer 3 is provided) is, for example, 30° C. or higher, and for example, 60° C. or lower.

[0101] Thus, the copper layer 4 is arranged on one surface in the thickness direction of the inorganic layer 3 .

[0102] Through the above, the conductive film 1 is manufactured.

[0103] [Second method]

[0104] In the second method, oxygen is not supplied in the second step, and oxygen is supplied in the third step.

[0105] In the third step, as a method of supplying oxygen, the following methods can be listed: Method 2A, firstly, by sputtering, an inert gas and oxygen are supplied to configure a portion of the copper layer 4 (hereinafter referred to as the first copper layer 4A) on one surface in the thickness direction of the inorganic layer 3, and then by sputtering, an inert gas is supplied without oxygen, and the remaining portion of the copper layer 4 (hereinafter referred to as the second copper layer 4B) is configured on one surface in the thickness direction of the first copper layer 4A; and Method 2B, by sputtering, an inert gas and oxygen are supplied to configure the entire copper layer 4 on one surface in the thickness direction of the inorganic layer 3.

[0106] Hereinafter, the 2A method and the 2B method will be described in detail in sequence.

[0107] [Method 2A]

[0108] (First process)

[0109] In the first step, Figure 3AAs shown, an organic resin substrate 2 is prepared.

[0110] (Second process)

[0111] In the second step, Figure 3B As shown, the inorganic layer 3 is disposed on one surface in the thickness direction of the organic resin substrate 2 by sputtering.

[0112] In the sputtering method, an inert gas is supplied as a sputtering gas, and oxygen gas is not supplied.

[0113] The gas pressure, power supply, and discharge output during sputtering are the same as those during sputtering in the second step of the first method.

[0114] Thus, the inorganic layer 3 is disposed on one surface in the thickness direction of the organic resin substrate 2 .

[0115] (Third process)

[0116] In the third step, the first copper layer 4A is arranged on one surface of the inorganic layer 3 in the thickness direction by supplying an inert gas and oxygen by sputtering, and then the first copper layer 4B is arranged on one surface of the first copper layer 4A in the thickness direction by supplying an inert gas without supplying oxygen by sputtering.

[0117] That is, the third step includes: step 3A, in which an inert gas and oxygen are supplied by sputtering to configure a first copper layer 4A on one surface in the thickness direction of the inorganic layer 3; and step 3B, in which an inert gas is supplied without supplying oxygen to configure a second copper layer 4B on one surface in the thickness direction of the first copper layer 4A by sputtering.

[0118] In this case, copper layer 4 is composed of first copper layer 4A formed by sputtering with inert gas and oxygen gas supplied, and second copper layer 4B formed by sputtering with inert gas and no oxygen gas supplied.

[0119] (Step 3A)

[0120] In step 3A, if Figure 3C As shown, the first copper layer 4A is arranged on one surface in the thickness direction of the inorganic layer 3 by sputtering while supplying an inert gas and oxygen gas.

[0121] The flow rate of the oxygen gas is, for example, 1 sccm or more, preferably 3 sccm or more, more preferably 7 sccm or more, and is, for example, 20 sccm or less, preferably 15 sccm or less.

[0122] Furthermore, the flow rate ratio of the flow rate of the inert gas to the flow rate of the oxygen gas is, for example, 40 or more, and for example, 150 or less.

[0123] The gas pressure, power supply, and film formation temperature during sputtering are the same as those during sputtering in the third step of the first method.

[0124] The discharge output is, for example, 5.0 kW or more, preferably 10.0 kW or more, and, for example, 20 kW or less.

[0125] Thus, the first copper layer 4A is arranged on one surface in the thickness direction of the inorganic layer 3 .

[0126] The thickness of the first copper layer 4A is, for example, not less than 5 nm, and, for example, not more than 20 nm.

[0127] (Step 3B)

[0128] In step 3B, if Figure 3D As shown, the second copper layer 4B is disposed on one surface in the thickness direction of the first copper layer 4A by sputtering while supplying an inert gas and not supplying oxygen.

[0129] The gas pressure, power supply, discharge output, and film formation temperature during sputtering are the same as those during sputtering in the third step of the first method.

[0130] Thus, the second copper layer 4B is arranged on one surface in the thickness direction of the first copper layer 4A.

[0131] The thickness of the second copper layer 4B is, for example, not less than 50 nm, and, for example, not more than 300 nm.

[0132] Through the above, the copper layer 4 is disposed on one surface in the thickness direction of the inorganic layer 3 to produce the conductive film 1 .

[0133] [Method 2B]

[0134] (First process)

[0135] In the first step, Figure 2A As shown, an organic resin substrate 2 is prepared.

[0136] (Second process)

[0137] In the second step, Figure 2B As shown, the inorganic layer 3 is disposed on one surface in the thickness direction of the organic resin substrate 2 by sputtering.

[0138] In the sputtering method, an inert gas is supplied as a sputtering gas, and oxygen gas is not supplied.

[0139] The gas pressure, power supply, and discharge output during sputtering are the same as those during sputtering in the second step of the first method.

[0140] Thus, the inorganic layer 3 is disposed on one surface in the thickness direction of the organic resin substrate 2 .

[0141] (Third process)

[0142] In the third step, Figure 2C As shown, the copper layer 4 is arranged on one surface in the thickness direction of the inorganic layer 3 by sputtering while supplying an inert gas and oxygen gas.

[0143] In such a case, the copper layer 4 does not include a copper layer formed by a sputtering method in which an inert gas is supplied but oxygen is not supplied, but is composed of a copper layer formed by a sputtering method in which an inert gas is supplied and oxygen is supplied.

[0144] The oxygen flow rate, the flow ratio of the inert gas to the oxygen flow rate, the gas pressure, the power supply, the discharge output and the film forming temperature during sputtering are the same as those of the oxygen flow rate, the flow ratio of the inert gas to the oxygen flow rate, the gas pressure, the power supply, the discharge output and the film forming temperature during sputtering in the 3A process in the above-mentioned 2A method.

[0145] Thus, the copper layer 4 is arranged on one surface in the thickness direction of the inorganic layer 3 .

[0146] Through the above, the conductive film 1 is manufactured.

[0147] [Third Method]

[0148] In the third method, oxygen is supplied in the second step and the third step.

[0149] In addition, in the third method, as a method for supplying oxygen in the third step, the following can be listed: the 3A method, firstly, by sputtering, an inert gas and oxygen are supplied to configure the first copper layer 4A on one surface in the thickness direction of the inorganic layer 3, and then by sputtering, an inert gas is supplied without oxygen, and the second copper layer 4B is configured on one surface in the thickness direction of the first copper layer 4A; and the 3B method, by sputtering, an inert gas and oxygen are supplied to configure the entire copper layer 4 on one surface in the thickness direction of the inorganic layer 3.

[0150] Hereinafter, method 3A and method 3B will be described in detail in sequence.

[0151] [Method 3A]

[0152] (First process)

[0153] In the first step, Figure 3A As shown, an organic resin substrate 2 is prepared.

[0154] (Second process)

[0155] In the second step, Figure 3B As shown, the inorganic layer 3 is disposed on one surface in the thickness direction of the organic resin substrate 2 by sputtering.

[0156] In the sputtering method, an inert gas is supplied as a sputtering gas, and oxygen is supplied.

[0157] The flow rate of oxygen gas is, for example, greater than 10 sccm, preferably greater than 30 sccm, and, for example, less than 200 sccm, preferably less than 150 sccm, more preferably less than 100 sccm, further preferably less than 80 sccm, and particularly preferably less than 60 sccm.

[0158] Furthermore, the flow rate ratio of the flow rate of the inert gas to the flow rate of the oxygen gas is, for example, 40 or more, and for example, 150 or less.

[0159] The gas pressure, power supply, and discharge output during sputtering are the same as those during sputtering in the second step of the first method.

[0160] Thus, the inorganic layer 3 is disposed on one surface in the thickness direction of the organic resin substrate 2 .

[0161] (Step 3A)

[0162] In step 3A, if Figure 3C As shown, the first copper layer 4A is arranged on one surface in the thickness direction of the inorganic layer 3 by sputtering while supplying an inert gas and oxygen gas.

[0163] The oxygen flow rate is less than that of the second step in the above-mentioned method 3A, for example, greater than 1 sccm, preferably greater than 3 sccm, more preferably greater than 5 sccm, and for example, less than 20 sccm, preferably less than 15 sccm, more preferably less than 8 sccm.

[0164] Furthermore, the flow rate ratio of the flow rate of the inert gas to the flow rate of the oxygen gas is, for example, 40 or more, and for example, 500 or less.

[0165] The gas pressure, power supply, discharge output and film formation temperature during sputtering are the same as those during sputtering in the 3A step in the 2A method described above.

[0166] Thus, the first copper layer 4A is arranged on one surface in the thickness direction of the inorganic layer 3 .

[0167] (Step 3B)

[0168] In step 3B, if Figure 3DAs shown, the second copper layer 4B is disposed on one surface in the thickness direction of the first copper layer 4A by sputtering while supplying an inert gas and not supplying oxygen.

[0169] The gas pressure, power supply, and discharge output during sputtering are the same as those during sputtering in the third step of the first method.

[0170] Thus, the second copper layer 4B is arranged on one surface in the thickness direction of the first copper layer 4A.

[0171] Through the above, the copper layer 4 is disposed on one surface in the thickness direction of the inorganic layer 3 to produce the conductive film 1 .

[0172] [Method 3B]

[0173] (First process)

[0174] In the first step, Figure 2A As shown, an organic resin substrate 2 is prepared.

[0175] (Second process)

[0176] In the second step, Figure 2B As shown, the inorganic layer 3 is disposed on one surface in the thickness direction of the organic resin substrate 2 by sputtering.

[0177] In the sputtering method, an inert gas is supplied as a sputtering gas, and oxygen is supplied.

[0178] The gas pressure, power supply, and discharge output during sputtering are the same as those during sputtering in the second step of the first method.

[0179] Thus, the inorganic layer 3 is disposed on one surface in the thickness direction of the organic resin substrate 2 .

[0180] (Third process)

[0181] In the third step, Figure 2C As shown, the copper layer 4 is arranged on one surface in the thickness direction of the inorganic layer 3 by sputtering while supplying an inert gas and oxygen gas.

[0182] The oxygen flow rate, the flow ratio of the inert gas to the oxygen flow rate, the gas pressure, the power supply, the discharge output and the film forming temperature during sputtering are the same as those of the oxygen flow rate, the flow ratio of the inert gas to the oxygen flow rate, the gas pressure, the power supply, the discharge output and the film forming temperature during sputtering in the 3A process in the above-mentioned 3A method.

[0183] Thus, the copper layer 4 is arranged on one surface in the thickness direction of the inorganic layer 3 .

[0184] Through the above, the conductive film 1 is manufactured.

[0185] As a method for producing the conductive film 1 , from the viewpoint of further reducing the specific resistance of the copper layer 4 , preferably, the 3A method is used.

[0186] <Y in the conductive film>

[0187] In the conductive film 1, Y calculated according to the following formula (1) is less than 23.200, preferably 23.000 or less, more preferably 22.500 or less, further preferably 22.000 or less, particularly preferably 21.500 or less, most preferably 21.000 or less, further preferably 20.500 or less, and for example, 10.000 or more.

[0188] Y=-0.0002243×(α 111 / t)+5.764×β 111 -0.02178×γ 111 -0.02283×(α 200 / t)

[0189] -0.009098×γ 200 +0.01051×t+28.15……(1)

[0190] In the above formula (1), α 111 It represents the integrated intensity of the peak of the (111) plane of the copper layer 4 in the out-of-plane diffraction measurement by the X-ray diffraction method. The measurement method of the out-of-plane diffraction measurement by the X-ray diffraction method will be described in detail in the examples described later (the same applies hereinafter).

[0191] t represents the thickness of the copper layer 4 (nm).

[0192] β 111 It represents the integrated intensity ratio of the integrated intensity of the peak of the (111) plane of the copper layer 4 in the out-of-plane diffraction measurement of the X-ray diffraction method to the integrated intensity of all the peaks of the copper layer 4. It should be noted that the integrated intensity of all the peaks of the copper layer 4 refers to the total amount of the integrated intensity of the peak of the (111) plane, the integrated intensity of the peak of the (200) plane, the integrated intensity of the peak of the (311) plane, and the integrated intensity of the peak of the (222) plane.

[0193] γ 111 The crystallite size of the (111) plane of the copper layer 4 measured by out-of-plane diffraction using an X-ray diffraction method is shown in FIG. Specifically, the crystallite size of the (111) plane of the copper layer 4 is, for example, Above, preferably More preferably Above, in addition, for example The following are preferably The following are more preferably the following.

[0194] It should be noted that the crystallite size of the (111) plane of the copper layer 4 can be calculated according to the Scherrer formula (crystallite size = Kλ / βcosθ, K: Scherrer constant, λ: X-ray wavelength, β: half-width, θ: Bragg angle) (the same applies below).

[0195] α 200 This shows the integrated intensity of the peak of the (200) plane of the copper layer 4 in the out-of-plane diffraction measurement by the X-ray diffraction method.

[0196] γ 200 The crystallite size of the (200) plane of the copper layer 4 measured by out-of-plane diffraction using an X-ray diffraction method is shown in FIG. Specifically, the crystallite size of the (200) plane of the copper layer 4 is, for example, Above, preferably More preferably Above, in addition, for example The following are preferably The following are more preferably the following.

[0197] In addition, the above formula (1) is derived based on the simulation described in detail in the examples described later.

[0198] In addition, Y can be adjusted to the above range according to the flow rate of oxygen in the second step and the flow rate of oxygen in the third step, for example.

[0199] <Effects>

[0200] The conductive film 1 includes the inorganic layer 3 . Therefore, when the conductive film 1 is produced, outgassing from the organic resin substrate 2 can be blocked.

[0201] Specifically, during the production of the conductive film 1, outgassing may occur from the organic resin substrate 2. Due to such outgassing, copper oxide is formed on the other surface in the thickness direction of the copper layer 4. This may reduce the adhesion between the organic resin substrate 2 and the copper layer 4.

[0202] On the other hand, the conductive film 1 includes the inorganic layer 3. This can isolate the above-mentioned outgassing. In this way, the formation of copper oxide on the other side of the copper layer 4 in the thickness direction can be suppressed, and as a result, the decrease in the adhesion between the organic resin substrate 2 (inorganic layer 3) and the copper layer 4 can be suppressed.

[0203] Furthermore, Y calculated from the above formula (1) of the conductive film 1 is less than 23.200. Therefore, the specific resistance of the copper layer 4 can be reduced.

[0204] In detail, as described above, from the viewpoint of suppressing the decrease in adhesion, if the inorganic layer 3 is provided, the crystal growth of the (200) plane of the copper layer in the out-of-plane diffraction measurement of the X-ray diffraction method is hindered. In this way, the crystal grains become smaller and the crystal interface that hinders the movement of electrons increases. As a result, the specific resistance becomes higher.

[0205] On the other hand, in the conductive film 1, Y calculated by the above formula (1) is less than 23.200. In this case, in the copper layer 4, the crystal growth of the (200) plane proceeds appropriately, and the crystal grains can be enlarged, so that the specific resistance of the copper layer 4 can be reduced.

[0206] <Modification>

[0207] In the modification, the same reference numerals are given to the same components and processes as those in one embodiment, and their detailed description is omitted. In addition, the modification can play the same role and effect as the first embodiment unless otherwise specified. Moreover, one embodiment and its modification can be appropriately combined.

[0208] In the above description, the conductive film 1 includes, in order in the thickness direction: an organic resin substrate 2, an inorganic layer 3, and a copper layer 4, but a functional layer (such as a hard coating layer) may be disposed between the organic resin substrate 2 and the inorganic layer 3. In this case, the conductive film 1 includes, in order in the thickness direction: an organic resin substrate 2, a hard coating layer, an inorganic layer 3, and a copper layer 4.

[0209] Example

[0210] The present invention is further specifically described by the following embodiments and comparative examples. It should be noted that the present invention is not limited to any embodiments and comparative examples. In addition, the specific numerical values ​​of the mixing ratio (containing ratio), physical property values, parameters, etc. used in the following description can be replaced by the upper limit value (defined as "below", "less than") or the lower limit value (defined as "above", "greater than") corresponding to the mixing ratio (containing ratio), physical property values, parameters, etc. recorded in the above-mentioned "specific embodiments" corresponding to them.

[0211] <Manufacturing of conductive film>

[0212] Example 1

[0213] The conductive film was produced by the first method. Specifically, the conductive film was produced by the following procedure.

[0214] [First process]

[0215] Polyethylene terephthalate (125U48, manufactured by Toray Industries, Inc., thickness 125 μm) was prepared as an organic resin substrate.

[0216] [Second step]

[0217] An inorganic layer (thickness 5 nm) was disposed on one surface in the thickness direction of the organic resin substrate by sputtering under the following conditions.

[0218] {condition}

[0219] Equipment: Roll-to-roll sputtering film forming equipment (wind-up DC magnetron sputtering equipment).

[0220] Material of the inorganic layer: ITO.

[0221] Gas: argon gas and oxygen gas (oxygen flow rate: 50 sccm), flow ratio of the inert gas flow rate to the oxygen flow rate: 14.

[0222] Discharge output: 7.2kW.

[0223] Air pressure in the film forming chamber: 0.4Pa.

[0224] Travel speed: 8.0m / min.

[0225] [Third step]

[0226] A copper layer (104.6 nm) was disposed on one surface in the thickness direction of the inorganic layer by sputtering under the following conditions.

[0227] {condition}

[0228] Equipment: Roll-to-roll sputtering film forming equipment (wind-up DC magnetron sputtering equipment).

[0229] Gas: Argon.

[0230] Discharge output: 100kW.

[0231] Air pressure in the film forming chamber: 0.4Pa.

[0232] Film forming temperature: 40℃.

[0233] Travel speed: 8.0m / min.

[0234] Embodiment 2 to Embodiment 5

[0235] A conductive film was produced in the same procedure as in Example 1. However, based on the description in Table 1, the flow rate of the inorganic layer and the oxygen gas and the thickness of the copper layer were changed.

[0236] Example 6

[0237] The conductive film was manufactured by the 2A method. Specifically, the conductive film was manufactured by the following procedure.

[0238] [First process]

[0239] Polyethylene terephthalate (125U48, manufactured by Toray Industries, Inc., thickness 125 μm) was prepared as an organic resin substrate.

[0240] [Second step]

[0241] An inorganic layer (thickness 5 nm) was disposed on one surface in the thickness direction of the organic resin substrate by sputtering under the following conditions.

[0242] {condition}

[0243] Equipment: Roll-to-roll sputtering film forming equipment (wind-up DC magnetron sputtering equipment).

[0244] Material of the inorganic layer: ITO.

[0245] Gas: Argon.

[0246] Discharge output: 7.2kW.

[0247] Air pressure in the film forming chamber: 0.4Pa.

[0248] Travel speed: 8.0m / min.

[0249] [Step 3A]

[0250] A first copper layer (thickness: 12 nm) was disposed on one surface in the thickness direction of the inorganic layer by sputtering under the following conditions.

[0251] {condition}

[0252] Equipment: Roll-to-roll sputtering film forming equipment (wind-up DC magnetron sputtering equipment).

[0253] Gas: argon and oxygen (oxygen flow rate: 5 sccm), flow ratio of the inert gas to the oxygen flow rate: 5.

[0254] Discharge output: 14.7kW.

[0255] Air pressure in the film forming chamber: 0.4Pa.

[0256] Film forming temperature: 40℃.

[0257] Travel speed: 8.0m / min.

[0258] [Step 3B]

[0259] A second copper layer (thickness: 92 nm) was disposed on one surface in the thickness direction of the first copper layer by sputtering under the following conditions.

[0260] {condition}

[0261] Equipment: Roll-to-roll sputtering film forming equipment (wind-up DC magnetron sputtering equipment).

[0262] Gas: Argon.

[0263] Discharge output: 100kW.

[0264] Air pressure in the film forming chamber: 0.4Pa.

[0265] Film forming temperature: 40℃.

[0266] Travel speed: 8.0m / min.

[0267] Example 7

[0268] A conductive film was produced according to the same procedure as in Example 6. However, the flow rate of oxygen gas was changed according to the description in Table 1.

[0269] Example 8

[0270] The conductive film was manufactured by the 3A method. Specifically, the conductive film was manufactured by the following procedure.

[0271] [First process]

[0272] Polyethylene terephthalate (125U48, manufactured by Toray Industries, Inc., thickness 125 μm) was prepared as an organic resin substrate.

[0273] [Second step]

[0274] An inorganic layer (thickness 5 nm) was disposed on one surface in the thickness direction of the organic resin substrate by sputtering under the following conditions.

[0275] {condition}

[0276] Equipment: Roll-to-roll sputtering film forming equipment (wind-up DC magnetron sputtering equipment).

[0277] Material of the inorganic layer: ITO.

[0278] Gas: argon gas and oxygen gas (oxygen flow rate: 20 sccm), flow ratio of the inert gas flow rate to the oxygen flow rate: 35.

[0279] Discharge output: 7.2kW.

[0280] Air pressure in the film forming chamber: 0.4Pa.

[0281] Travel speed: 8.0m / min.

[0282] [Step 3A]

[0283] A first copper layer (thickness: 12 nm) was disposed on one surface in the thickness direction of the inorganic layer by sputtering under the following conditions.

[0284] {condition}

[0285] Equipment: Roll-to-roll sputtering film forming equipment (wind-up DC magnetron sputtering equipment).

[0286] Gas: argon gas and oxygen gas (oxygen flow rate: 7 sccm); the flow rate ratio of the inert gas to the oxygen flow rate is 100.

[0287] Discharge output: 14.7kW.

[0288] Air pressure in the film forming chamber: 0.4Pa.

[0289] Film forming temperature: 40℃.

[0290] Travel speed: 8.0m / min.

[0291] [Step 3B]

[0292] A second copper layer (thickness: 92 nm) was disposed on one surface in the thickness direction of the first copper layer by sputtering under the following conditions.

[0293] {condition}

[0294] Equipment: Roll-to-roll sputtering film forming equipment (wind-up DC magnetron sputtering equipment).

[0295] Gas: Argon.

[0296] Discharge output: 100kW.

[0297] Air pressure in the film forming chamber: 0.4Pa.

[0298] Film forming temperature: 40℃.

[0299] Travel speed: 8.0m / min.

[0300] Embodiment 9 to Embodiment 13

[0301] A conductive film was produced according to the same procedure as in Example 8. However, based on the description in Table 1, the flow rate of oxygen gas and the thickness of the copper layer were changed.

[0302] Comparative Example 1

[0303] A conductive film was produced according to the same procedure as in Example 1. However, the flow rate of oxygen gas was changed according to the description in Table 1. Specifically, oxygen gas was not supplied in the second step.

[0304] <Evaluation>

[0305] (Surface resistance)

[0306] The surface resistance of the copper layer of each Example and each Comparative Example was measured by a four-probe method in accordance with JIS K7194. The results are shown in Table 1.

[0307] (Specific resistance)

[0308] The specific resistance of the copper layer of each Example and each Comparative Example was calculated by multiplying the surface resistance value by the thickness of the copper layer.

[0309] (Out-of-plane diffraction measurement by X-ray diffraction method)

[0310] Based on the following measurement conditions, an X-ray analyzer (SmartLab (Rigaku)) was used to perform out-of-plane diffraction measurement of the metal layer of each Example and each Comparative Example. 111 , β 111 , γ 111 , α 200 and γ 200 , and the results are shown in Table 1.

[0311] {Measurement conditions}

[0312] Scan axis: 2θ / θ.

[0313] Start angle (°): 10.

[0314] End angle (°): 100.

[0315] Step(°):0.02.

[0316] Speed( / min):1.0.

[0317] (Calculation of Y)

[0318] First, a conductive film is prepared to calculate the above formula (1) in the following order, and an out-of-plane diffraction measurement by X-ray diffraction method is performed. Thus, 14 experimental data (equivalent to the data of Examples 1 to 13 and Comparative Example 1) are obtained to establish the correspondence between the process conditions and the resistivity of the copper layer 4. Various explanatory variables are prepared based on the obtained experimental data, and ridge regression is performed. Ridge regression is a linear regression method with an L2 regularization term. Through ridge regression, the coefficients of the formula are optimized to improve the prediction accuracy. Thus, the above formula (1) is obtained. Substitute each parameter into the obtained formula (1) and calculate Y. The results are shown in Table 1.

[0319] <Investigation>

[0320] It is found that Examples 1 to 13 are provided with an inorganic layer, and therefore can block outgassing from the organic resin substrate.

[0321] Furthermore, it is found that, in the case of including an inorganic layer, Examples 1 to 13 in which Y is less than 23.200 can reduce the specific resistance as compared with Comparative Example 1 in which Y is 23.200 or more.

[0322] Specifically, in Examples 1 to 13 where Y is less than 23.200, the specific resistance can be 2.300×10 －8 Specifically, it was found that the practicability of achieving a specific resistance at a practical level can be ensured, particularly in various devices such as flat panel displays and touch panels, as a conductor layer for patterning electrodes.

[0323] [Table 1]

[0324]

[0325] It should be noted that the above invention is provided in the form of exemplary embodiments of the present invention, but these are merely examples and are not to be construed as limiting. Modifications of the present invention that are clear to those skilled in the art are included in the claims.

[0326] Industrial Applicability

[0327] The conductive film and the method for producing a conductive film of the present invention are preferably used for producing various devices such as touch panels and optical sensors.

[0328] Description of Reference Numerals

[0329] 1: Conductive film; 2: Organic resin substrate; 3: Inorganic layer; 4: Copper layer.

Claims

1. A conductive film, wherein: have: Organic resin substrate; an inorganic layer disposed on one side in the thickness direction of the organic resin substrate; and The copper layer is directly disposed on one surface of the inorganic layer in the thickness direction, wherein Y calculated according to the following formula (1) is less than 23.200, Y=-0.0002243×(a 111 / t)+5.764×β 111 -0.02178×γ 111 -0.02283×(a 200 / t)-0.009098×γ 200 +0.01051×t+28.15……(1) In the above formula (1), α 111 represents the integrated intensity of the peak of the (111) plane of the copper layer in the out-of-plane diffraction measurement of the X-ray diffraction method; t represents the thickness of the copper layer, in nm; β 111 represents the integrated intensity ratio of the integrated intensity of the peak of the (111) plane of the copper layer relative to the integrated intensity of all peaks of the copper layer in the out-of-plane diffraction measurement by the X-ray diffraction method; γ 111 It represents the crystallite size of the (111) plane of the copper layer in the out-of-plane diffraction measurement by X-ray diffraction method, and the unit is α 200 represents the integrated intensity of the peak of the (200) plane of the copper layer in the out-of-plane diffraction measurement by the X-ray diffraction method; γ 200 It represents the crystallite size of the (200) plane of the copper layer in the out-of-plane diffraction measurement by X-ray diffraction method, and the unit is 2. The conductive film according to claim 1, wherein The copper layer has a thickness of 50 nm or more.

3. The conductive film according to claim 1, wherein The copper layer has a thickness of less than 300 nm.

4. The conductive film according to any one of claims 1 to 3, wherein The thickness of the inorganic layer is greater than or equal to 2 nm and less than or equal to 15 nm.

5. A method for manufacturing a conductive film, comprising: The first step is to prepare an organic resin substrate; In the second step, an inorganic layer is disposed on one surface in the thickness direction of the organic resin substrate by sputtering; as well as In the third step, a copper layer is disposed on one surface in the thickness direction of the inorganic layer by sputtering. In at least one of the second step and the third step, an inert gas is supplied as a sputtering gas, and oxygen gas is supplied.

6. The method for producing a conductive film according to claim 5, wherein: In the second step, an inert gas is supplied as a sputtering gas, and oxygen is supplied. The flow rate of the oxygen gas in the second step is greater than or equal to 5 sccm and less than or equal to 200 sccm.

7. The method for producing a conductive film according to claim 5, wherein: In the third step, an inert gas is supplied as a sputtering gas, and oxygen is supplied. The third step comprises: a step 3A of providing a first copper layer on one side of the thickness direction of the inorganic layer by sputtering while supplying an inert gas and oxygen; and a step 3B of providing a second copper layer on one side of the thickness direction of the first copper layer by sputtering while supplying an inert gas and not supplying oxygen. The flow rate of the oxygen gas in the step 3A is not less than 1 sccm and not more than 20 sccm.

8. The method for producing a conductive film according to claim 5, wherein: In the second step and the third step, an inert gas is supplied as a sputtering gas, and oxygen is supplied. The third step comprises: a step 3A of providing a first copper layer on one side of the thickness direction of the inorganic layer by sputtering while supplying an inert gas and oxygen; and a step 3B of providing a second copper layer on one side of the thickness direction of the first copper layer by sputtering while supplying an inert gas and not supplying oxygen. The flow rate of oxygen in the second step is 10 sccm or more and 200 sccm or less. The flow rate of the oxygen gas in the step 3A is smaller than the flow rate of the oxygen gas in the second step and is greater than or equal to 1 sccm and less than or equal to 20 sccm.

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