Conductive film
By introducing an inorganic layer into the conductive film and optimizing the structure of the copper layer, the problems of increased resistivity and decreased adhesion caused by the barrier layer are solved, and efficient conductivity and stable adhesion are achieved.
Patent Information
- Application Number
- CN202380050036.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2023-01-11
- Filing Date
- 2023-05-12
- Publication Date
- 2025-02-14
AI Technical Summary
After the conventional conductive film is provided with the barrier layer, the resistivity of the copper layer becomes higher, and the adhesion between the base material and the metal layer decreases.
The conductive film structure with an inorganic layer is adopted, wherein the inorganic layer is arranged on the thickness direction side of the organic resin substrate, and the copper layer is arranged on the thickness direction side of the inorganic layer, and the inorganic layer is measured by energy dispersion X-ray analysis (EDX). The concentration of O in the copper layer near the layer is 1.4 atomic % or more and 15 atomic % or less relative to the sum of Cu, O and inorganic elements.
The contact between the organic resin substrate and the copper layer is effectively suppressed, the adhesion is prevented from decreasing, and the resistivity of the copper layer is reduced, thereby achieving excellent electrical conductivity.
Smart Images

Figure CN119451815A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a 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 sputtering.
[0004] On the other hand, in the manufacture of the above-mentioned conductive film, degassing from the substrate sometimes occurs. Due to such degassing, metal oxides are formed on the other side of the metal layer in the thickness direction. This may cause the adhesion between the substrate and the metal layer to decrease.
[0005] In view of this, a conductive film having a barrier layer (inorganic layer) between the substrate and the metal layer has been studied. The barrier layer can prevent outgassing from the substrate from contacting the metal layer, thereby eliminating the above-mentioned inconvenience.
[0006] As such a conductive film, a conductive film including a resin film, an inorganic 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, when the barrier layer is provided, there is a problem in that the resistivity of the metal layer (copper layer) increases.
[0012] The present invention provides a conductive film which can suppress outgassing from an organic resin substrate from coming into contact with a copper layer and has excellent resistivity.
[0013] Solutions for solving problems
[0014] The present invention [1] includes 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 in the copper layer near the inorganic layer, the element concentration of O relative to the sum of Cu, O and inorganic elements derived from the inorganic layer measured by energy dispersive X-ray analysis (EDX) is 1.4 atomic % or more and 15 atomic % or less.
[0015] The present invention [2] includes the conductive film described in the above [1], wherein the copper layer has a thickness of 50 nm or more.
[0016] The present invention [3] includes the conductive film described in [1] or [2] above, wherein the copper layer has a thickness of 300 nm or less.
[0017] 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.
[0018] Effects of the Invention
[0019] The conductive film of the present invention includes an inorganic layer. Therefore, when the conductive film is manufactured, it is possible to suppress outgassing from the organic resin substrate from coming into contact with the copper layer. As a result, it is possible to suppress a decrease in adhesion between the organic resin substrate and the copper layer.
[0020] Furthermore, in the conductive film of the present invention, in the copper layer near the inorganic layer, the element concentration of O relative to the sum of Cu, O and inorganic elements from the inorganic layer measured by energy dispersive X-ray analysis (EDX) is 1.4 atomic % or more and 15 atomic % or less. Therefore, the resistivity of the copper layer can be reduced. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Figure 1 One embodiment of the conductive film of the present invention is shown.
[0022] 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.
[0023] Figure 3 In Example 3, the element concentrations of Cu, O, and inorganic elements derived from the inorganic layer were measured in one direction along the thickness direction from the organic resin substrate to the copper layer by energy dispersive X-ray analysis (EDX).
[0024] Figure 4 yes Figure 3 A graph of the data.
[0025] Figure 5 In Comparative Example 1, the element concentrations of Cu, O, and inorganic elements derived from the inorganic layer were measured in one direction along the thickness direction from the organic resin substrate to the copper layer by energy dispersive X-ray analysis (EDX).
[0026] Figure 6 yes Figure 5 A graph of the data. DETAILED DESCRIPTION
[0027] 1. Conductive film
[0028] Reference Figure 1 , one embodiment of the conductive film of the present invention is described.
[0029] exist Figure 1 In the figure, the up-down direction of the paper is the up-down direction (thickness direction). In addition, the upper side of the paper is the upper side (one side in the thickness direction). In addition, the lower side of the paper is the lower side (the other side in the thickness direction). In addition, the left-right direction and the depth direction of the paper are the surface directions orthogonal to the up-down direction. Specifically, the direction arrows of each figure are used as a reference.
[0030] 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.
[0031] like Figure 1 As shown, the conductive film 1 comprises: an organic resin substrate 2; an inorganic layer 3, which is disposed on one side in the thickness direction of the organic resin substrate 2; and a copper layer 4, which is directly disposed on one side 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 disposed on the upper surface (one side in the thickness direction) of the organic resin substrate 2; and a copper layer 4, which is directly disposed on the upper surface (one side in the thickness direction) of the inorganic layer 3.
[0032] The thickness of the conductive film 1 is, for example, 1 μm or more, preferably 5 μm or more, and, for example, 300 μm or less, preferably 200 μm or less.
[0033] <Organic resin base material>
[0034] 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.
[0035] As the organic resin substrate 2, for example, a polymer film can be mentioned.
[0036] Examples of the material of the polymer film 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, and preferably polyester resins are used.
[0037] As a polyester resin, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate are mentioned, for example, and polyethylene terephthalate is preferably mentioned.
[0038] As a (meth)acrylic resin, polymethyl methacrylate is mentioned, for example.
[0039] Examples of the olefin resin include polyethylene, polypropylene, and cycloolefin polymers.
[0040] As a cellulose resin, cellulose triacetate is mentioned, for example.
[0041] 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, further preferably 50 μm or more, particularly preferably 100 μm or more, and, for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less.
[0042] The thickness of the organic resin substrate 2 can be measured using a micrometer (“DG-205” manufactured by PEACOCK).
[0043] Furthermore, the organic resin substrate 2 preferably has transparency. Specifically, the total light transmittance (JISK 7375-2008) of the organic resin substrate 2 is, for example, 80% or more, or preferably 85% or more.
[0044] <Inorganic layer>
[0045] The inorganic layer 3 is a layer for preventing outgassing from the organic resin substrate 2 from coming into contact with the copper layer 4 in the method for producing the conductive film 1 described later.
[0046] 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.
[0047] The inorganic layer 3 will be described in detail later, but is formed by a sputtering method and is therefore a sputtered layer.
[0048] The material of the inorganic layer 3 is not particularly limited as long as it is an inorganic substance other than pure metallic copper. Specifically, preferred materials for the inorganic layer 3 include metals (excluding pure metallic copper) and metal oxides (excluding copper oxide).
[0049] Examples of the metal include Ni, In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Pd, and W, alloys of these metals, and alloys of these metals and copper.
[0050] 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).
[0051] Furthermore, the metal oxide may be either crystalline or amorphous.
[0052] As a material of the inorganic layer 3, metal oxides are preferably used.
[0053] The material of the inorganic layer 3 may be used alone or in combination of two or more.
[0054] The thickness of the inorganic layer 3 is, for example, 2 nm or more from the viewpoint of gas barrier properties, and is, for example, 15 nm or less, preferably 10 nm or less, and more preferably 7 nm or less from the viewpoint of processability.
[0055] 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.
[0056] <Copper layer>
[0057] The copper layer 4 is a conductor layer and is formed into a desired pattern as required.
[0058] 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.
[0059] The copper layer 4 will be described in detail later, but is formed by sputtering and is therefore a sputtered layer.
[0060] Examples of the material of the copper layer 4 include copper (copper in the form of pure metal) and copper alloys.
[0061] The metal constituting the copper alloy is not particularly limited, and examples thereof include silver, tin, chromium, and zirconium.
[0062] As a material of the copper layer 4, copper (pure metal copper) is preferably used from the viewpoint of electrical conductivity. That is, the copper layer 4 is preferably composed of copper (pure metal copper).
[0063] The resistivity of the copper layer 4 is, for example, 2.300×10 -8 Ω·m or less, preferably 2.280×10 -8 Ω·m or less, more preferably 2.200×10 -8 Ω·m or less, and usually 1.000×10 -8 Ω·m or more.
[0064] In addition, the resistivity can be calculated by multiplying the surface resistance value measured by the four-probe method according to JIS K7194 by the thickness of the copper layer 4 .
[0065] The surface resistance value of the copper layer 4 is, for example, 0.222 Ω / □ or less, preferably 0.220 Ω / □ or less, and more preferably 0.210 Ω / □ or less.
[0066] 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 more than 0Ω / □.
[0067] In addition, the surface resistance value can be measured by a four-probe method in accordance with JIS K7194.
[0068] The thickness of the copper layer 4 is, for example, 50 nm or more, preferably 70 nm or more, more preferably 90 nm or more, and further preferably 100 nm or more from the viewpoint of resistance value, and is, for example, 300 nm or less, preferably 250 nm or less, more preferably 200 nm or less, further preferably 150 nm or less, and particularly preferably 120 nm or less from the viewpoint of productivity.
[0069] In the copper layer 4 near the inorganic layer 3, the element concentration of O relative to the sum of Cu (copper element), O (oxygen element) and inorganic elements from the inorganic layer 3 measured by energy dispersive X-ray analysis (EDX) is 1.4 atomic % or more, preferably 2.0 atomic % or more, more preferably 2.5 atomic % or more, further preferably 3.0 atomic % or more, and particularly preferably 4.0 atomic % or more, and is 15 atomic % or less, preferably 10 atomic % or less, more preferably 7 atomic % or less, and further preferably 5 atomic % or less.
[0070] In addition, the measurement method and measurement conditions of the element concentration by energy dispersive X-ray analysis (EDX) are described in detail in the examples described later.
[0071] The copper layer 4 near the inorganic layer 3 refers to the copper layer 4 at the initial moment when the element concentration of Cu, O and inorganic elements from the inorganic layer 3 is measured in one direction along the thickness direction from the organic resin substrate 2 to the copper layer 4 by energy dispersive X-ray analysis (EDX), and the element concentration of Cu relative to the sum of Cu, O and inorganic elements from the inorganic layer 3 is greater than 50 atomic %, and the element concentration of inorganic elements relative to the sum of Cu and inorganic elements from the inorganic layer 3 is less than 1 atomic %.
[0072] When the element concentration of O relative to the total of Cu, O and inorganic elements derived from the inorganic layer 3 in the copper layer 4 near the inorganic layer 3 measured by energy dispersive X-ray analysis (EDX) is within the above range, the resistivity of the copper layer 4 is excellent.
[0073] 2. Method for producing conductive film
[0074] Reference Figure 2A to Figure 2C , a method for manufacturing the conductive film 1 is described.
[0075] The method for producing the conductive film 1 comprises: a first step of preparing an organic resin substrate 2; a second step of disposing an inorganic layer 3 on one side in the thickness direction of the organic resin substrate 2 by sputtering; and a third step of disposing a copper layer 4 on one side in the thickness direction of the inorganic layer 3 by sputtering. In this method, the layers are sequentially disposed, for example, in a roll-to-roll manner. 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.
[0076] In the method for producing the conductive film 1 , in the second step and the third step, the sputtering method is performed while supplying the sputtering gas.
[0077] In the method for producing the conductive film 1, in the second step, for example, an inert gas (described later) is supplied as a sputtering gas. Preferably, in the second step, an inert gas (described later) and oxygen gas are supplied as a sputtering gas.
[0078] In the method for manufacturing the conductive film 1, in the third step, a target material, sputtering conditions, etc. are appropriately set to perform sputtering a plurality of times in order to form the desired copper layer 4. In the third step, the number of sputterings is, for example, two or more times, preferably four or more times, and, for example, twenty or less times, preferably ten or less times.
[0079] In the method for manufacturing the conductive film 1, in the third step, for example, an inert gas (described later) is supplied as a sputtering gas. Preferably, in the first sputtering of the third step, an inert gas (described later) and oxygen are supplied as a sputtering gas, and in the second and subsequent sputterings of the third step, only an inert gas (described later) is supplied as a sputtering gas.
[0080] That is, in the method for manufacturing the conductive film 1, for example, in the second step, the inert gas and oxygen are supplied together by sputtering, and the inorganic layer 3 is arranged on one side in the thickness direction of the organic resin substrate 2, and in the third step, only the inert gas is supplied by sputtering, and the copper layer 4 is arranged on one side in the thickness direction of the inorganic layer 3. In addition, for example, in the second step, only the inert gas is supplied by sputtering, and the inorganic layer 3 is arranged on one side in the thickness direction of the organic resin substrate 2, and in the third step, in the first sputtering, the inert gas and oxygen are supplied together by sputtering, and in the second and subsequent sputtering, only the inert gas is supplied, and the copper layer 4 is arranged on one side in the thickness direction of the inorganic layer 3. Furthermore, for example, in the second step, an inert gas and oxygen are supplied together by sputtering, and the inorganic layer 3 is arranged on one side in the thickness direction of the organic resin substrate 2. In the third step, an inert gas and oxygen are supplied together by sputtering in the first sputtering, and only an inert gas is supplied in the second and subsequent sputterings, and the copper layer 4 is arranged on one side in the thickness direction of the inorganic layer 3. Preferably, in the method for manufacturing the conductive film 1, in the second step, an inert gas and oxygen are supplied together by sputtering, and the inorganic layer 3 is arranged on one side in the thickness direction of the organic resin substrate 2. In the third step, an inert gas and oxygen are supplied together by sputtering in the first sputtering, and only an inert gas is supplied in the second and subsequent sputterings, and the copper layer 4 is arranged on one side in the thickness direction of the inorganic layer 3.
[0081] In the following description, a method for producing the conductive film 1 is described in detail.
[0082] [First process]
[0083] In the first step, Figure 2A As shown, an organic resin substrate 2 is prepared.
[0084] [Second step]
[0085] 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.
[0086] In order to arrange the inorganic layer 3 on one surface in the thickness direction of the organic resin substrate 2 by the sputtering method, first, the one surface in the thickness direction of the organic resin substrate 2 is subjected to a surface treatment as required.
[0087] Examples of the surface treatment include corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow treatment, and saponification treatment.
[0088] 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 of a sputtering film forming device. Then, a sputtering gas is supplied and a voltage is applied from a power supply, thereby accelerating gas ions and irradiating them to the target, and the target material is ejected 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.
[0089] In addition, as the sputtering gas, for example, only an inert gas (for example, argon gas) or an inert gas and oxygen gas may be supplied. Preferably, an inert gas and oxygen gas are supplied as the sputtering gas.
[0090] When an inert gas and oxygen are supplied together, the flow rate of oxygen is, for example, greater than 5 sccm, preferably greater than 10 sccm, more preferably greater than 20 sccm, further preferably greater than 30 sccm, particularly preferably greater than 40 sccm, and, for example, less than 200 sccm, preferably less than 100 sccm.
[0091] In addition, when an inert gas and oxygen are supplied together, the flow rate ratio of the inert gas to the flow rate of oxygen is, for example, greater than 3.5, preferably greater than 10, and, for example, less than 200, preferably less than 100, more preferably less than 50, and further preferably less than 30.
[0092] 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, preferably 1.0 Pa or less.
[0093] The power source may be, for example, a DC (Direct Current) power source, an AC (Alternating Current) power source, an MF (Middle Frequency) power source, or an RF (Radio Frequency) power source, or a combination of these power sources.
[0094] The discharge power is, for example, 1.0 kW or more, preferably 5.0 kW or more, and, for example, 20 kW or less.
[0095] Thus, the inorganic layer 3 is disposed on one surface in the thickness direction of the organic resin substrate 2 .
[0096] [Third step]
[0097] 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.
[0098] 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, thereby accelerating gas ions and irradiating them to the target, and the target material is ejected 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.
[0099] In the third step, the target material, sputtering conditions, etc. are appropriately set to perform multiple sputtering in order to form the desired copper layer 4. In the third step, the number of sputtering is, for example, two or more times, preferably four or more times, and, for example, twenty or less times, preferably ten or less times.
[0100] In addition, as the sputtering gas, for example, only an inert gas (such as argon) is supplied, or an inert gas and oxygen are supplied. More specifically, as the sputtering gas, for example, only an inert gas is supplied in all sputtering, or, in the first sputtering, an inert gas and oxygen are supplied, and in the second and subsequent sputtering, only an inert gas is supplied. Preferably, as the sputtering gas, in the first sputtering, an inert gas and oxygen are supplied, and in the second and subsequent sputtering, only an inert gas is supplied.
[0101] When an inert gas and oxygen are supplied together, the flow rate of oxygen is less than the flow rate of oxygen in the above-mentioned second process, for example, 1 sccm or more, preferably 3 sccm or more, more preferably 5 sccm or more, and for example, 30 sccm or less, preferably 20 sccm or less, more preferably 15 sccm or less.
[0102] In addition, when an inert gas and oxygen are supplied together, the flow rate ratio of the inert gas to the flow rate of oxygen is, for example, greater than 20, preferably greater than 40, and, for example, less than 500, preferably less than 200, more preferably less than 100, and further preferably less than 50.
[0103] 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, preferably 1.0 Pa or less.
[0104] 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 may be a combination of these power sources.
[0105] The discharge power is, for example, 5.0 kW or more, preferably 10.0 kW or more, and, for example, 20 kW or less.
[0106] 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.
[0107] Thus, the copper layer 4 is formed on one surface in the thickness direction of the inorganic layer 3 .
[0108] In the copper layer 4 thus formed, the element concentration of O relative to the total of Cu, O and inorganic elements derived from the inorganic layer 3 measured by energy dispersive X-ray analysis (EDX) is 1.4 atomic % or more and 15 atomic % or less in the copper layer 4 near the inorganic layer 3.
[0109] In the above manner, the conductive film 1 is manufactured.
[0110] <Effects>
[0111] The conductive film 1 includes the inorganic layer 3 . Therefore, when the conductive film 1 is produced, it is possible to suppress outgassing from the organic resin substrate 2 from coming into contact with the copper layer 4 .
[0112] 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.
[0113] On the other hand, the conductive film 1 includes the inorganic layer 3. This can prevent the above-mentioned outgassing from contacting the copper layer 4. In this way, the formation of copper oxide on the other surface in the thickness direction of the copper layer 4 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.
[0114] In addition, in the copper layer 4 of the conductive film 1, the element concentration of O measured by energy dispersive X-ray analysis (EDX) relative to the total of Cu, O, and inorganic elements derived from the inorganic layer 3 is 1.4 atomic % or more and 15 atomic % or less in the copper layer 4 near the inorganic layer 3. Therefore, the resistivity of the copper layer 4 can be reduced.
[0115] <Modification>
[0116] In the variant, the same reference numerals are used for the same components and processes as those in one embodiment, and detailed description thereof is omitted. In addition, the variant can exert the same effects as those in the first embodiment except for special descriptions. Moreover, one embodiment and its variant can be appropriately combined.
[0117] In the above description, the conductive film 1 includes the organic resin substrate 2, the inorganic layer 3, and the copper layer 4 in this order in the thickness direction, but a functional layer (for example, 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 the organic resin substrate 2, the hard coating layer, the inorganic layer 3, and the copper layer 4 in this order in the thickness direction.
[0118] [Example]
[0119] Embodiment and comparative example are shown below, and the present invention is further specifically described.It should be noted that the present invention is not limited to any embodiment and comparative example.In addition, the specific numerical values such as the mixing ratio (containing ratio), physical property value, parameter 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", "exceeding") of the mixing ratio (containing ratio), physical property value, parameter, etc. corresponding to these numerical values recorded in the above-mentioned "specific embodiments".
[0120] <Manufacturing of conductive film>
[0121] Example 1
[0122] The conductive film was produced according to the following steps.
[0123] [First process]
[0124] As an organic resin substrate, polyethylene terephthalate (125U48, manufactured by TORAY CORPORATION, thickness 125 μm) was prepared.
[0125] [Second step]
[0126] An inorganic layer (ITO layer) (thickness 5 nm) was disposed on one surface in the thickness direction of the organic resin substrate by sputtering under the following conditions.
[0127] {condition}
[0128] Device: Roll-to-roll sputtering film forming device (winding type DC magnetron sputtering device).
[0129] Material of the inorganic layer: ITO.
[0130] Gas: Argon and oxygen (oxygen flow rate 20 sccm).
[0131] Flow rate ratio of the inert gas flow rate to the oxygen flow rate: 35.
[0132] Discharge power: 7.2kW.
[0133] Air pressure in the film forming chamber: 0.4Pa.
[0134] Travel speed: 8.0m / min.
[0135] [Third step]
[0136] A copper layer (104 nm) was arranged on one surface in the thickness direction of the inorganic layer by sputtering under the following conditions. It should be noted that sputtering was performed eight times until the desired thickness was reached.
[0137] {condition}
[0138] Device: Roll-to-roll sputtering film forming device (winding type DC magnetron sputtering device).
[0139] Gas: Argon.
[0140] Discharge power: 14.7kW.
[0141] Air pressure in the film forming chamber: 0.4Pa.
[0142] Film forming temperature: 40℃.
[0143] Travel speed: 8.0m / min.
[0144] It should be noted that after the sputtering in the second step, the first sputtering in the third step is performed continuously.
[0145] Example 2
[0146] A conductive film was produced according to the same procedure as in Example 1. However, based on the description in Table 1, the flow rate of oxygen in the second step was changed.
[0147] Example 3
[0148] The first step and the second step were performed in the same manner as in Example 2, and the third step was performed in the following manner to produce a conductive film.
[0149] [Third step]
[0150] A copper layer (thickness 12 nm) was arranged on one surface in the thickness direction of the inorganic layer by sputtering under the following conditions. It should be noted that sputtering was performed only once.
[0151] {condition}
[0152] Device: Roll-to-roll sputtering film forming device (winding type DC magnetron sputtering device).
[0153] Gas: Argon and oxygen (oxygen flow rate 15 sccm).
[0154] Flow rate ratio of the inert gas flow rate to the oxygen flow rate: 47.
[0155] Discharge power: 14.7kW.
[0156] Air pressure in the film forming chamber: 0.4Pa.
[0157] Film forming temperature: 40℃.
[0158] Travel speed: 8.0m / min.
[0159] It should be noted that after the sputtering in the second step, the first sputtering in the third step is performed continuously.
[0160] Next, a copper layer (thickness 92 nm) was further deposited by sputtering under the following conditions. It should be noted that sputtering was performed seven times until the desired thickness was reached.
[0161] {condition}
[0162] Device: Roll-to-roll sputtering film forming device (winding type DC magnetron sputtering device).
[0163] Gas: Argon.
[0164] Discharge power: 14.7kW.
[0165] Air pressure in the film forming chamber: 0.4Pa.
[0166] Film forming temperature: 40℃.
[0167] Travel speed: 8.0m / min.
[0168] Comparative Example 1
[0169] 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, in the second step, oxygen gas was not supplied.
[0170] Comparative Example 2
[0171] A conductive film was produced according to the same procedure as in Example 3. However, the flow rate of oxygen gas was changed according to the description in Table 1. Specifically, in the third step, the flow rate of oxygen gas was set to 100 sccm (flow rate ratio of the inert gas flow rate to the oxygen flow rate: 7).
[0172] <Evaluation>
[0173] (Surface resistance)
[0174] 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.
[0175] (Resistivity)
[0176] The resistivity of the copper layer in each example and comparative example was calculated by multiplying the surface resistance value by the thickness of the copper layer.
[0177] (Element concentration of O)
[0178] In each embodiment and each comparative example, a sample was prepared using a focused ion beam device (FIB) using a microsampling method. The preparation apparatus and conditions are shown below. Next, a field emission analytical transmission electron microscope (FE-TEM) was used to observe the cross section of the prepared sample, and then, the element concentrations of Cu, O, and inorganic elements from the inorganic layer were measured along the thickness direction from the organic resin substrate by energy dispersive X-ray analysis (EDX). The apparatus and conditions used for observation and measurement are shown below. The element concentration of O in the copper layer near the inorganic layer relative to the sum of Cu, O, and inorganic elements from the inorganic layer 3 is shown in Table 1. In addition, the data of the element concentrations of Cu, O, and inorganic elements from the inorganic layer measured along the thickness direction from the organic resin substrate by energy dispersive X-ray analysis (EDX) in Example 3 and Comparative Example 1 and their graphs are shown in Figure 3 to Figure 6 .
[0179] {Device and Conditions}
[0180] FIB (FB2200, manufactured by Hitachi), accelerating voltage: 10 to 40 kV.
[0181] FE-TEM (JEM-2800, manufactured by JEOL Ltd.), accelerating voltage: 200 kV.
[0182] EDX (detector: JED-2300T (SD100GV), manufactured by JEOL), (analyzer: NORAN System 7, manufactured by Thermo Fisher Scientific), (analysis software: NSS, manufactured by Thermo Fisher Scientific).
[0183] <Investigation>
[0184] It is understood that since Examples 1 to 3 and Comparative Examples 1 and 2 include an inorganic layer, outgassing from the organic resin substrate can be suppressed from contacting the copper layer.
[0185] also, Figure 3 The data of element concentrations of Cu, O, and inorganic elements from the inorganic layer measured along the thickness direction from the organic resin substrate to the copper layer in Example 3 are shown. Figure 4 The graph is shown. When the moving distance from the organic resin substrate to one direction in the thickness direction is 13.2 μm, the element concentration of the inorganic element increases, thereby confirming that the organic resin substrate is switched to the inorganic layer. Moreover, when the moving distance from the organic resin substrate to one direction in the thickness direction is 23.1 μm, the element concentration of Cu increases, thereby confirming that the inorganic layer is switched to the copper layer.
[0186] The copper layer near the inorganic layer refers to the copper layer at the initial moment when the element concentration of Cu relative to the sum of Cu, O and inorganic elements from the inorganic layer is 50 atomic % or more and the element concentration of inorganic elements relative to the sum of Cu and inorganic elements from the inorganic layer is 1 atomic % or less. Figure 3 , when the moving distance from the organic resin substrate to one direction in the thickness direction is 26.4 μm, the element concentration of Cu relative to the sum of Cu, O and inorganic elements from the inorganic layer is 94.8 atomic %, and the element concentration of inorganic elements relative to the sum of Cu and inorganic elements from the inorganic layer is 0.54 atomic %, and the above conditions are met for the first time, so a copper layer near the inorganic layer is formed. That is, when the moving distance from the organic resin substrate to one direction in the thickness direction is 26.4 μm, the element concentration of O relative to the sum of Cu, O and inorganic elements from the inorganic layer is the element concentration of O in the copper layer near the inorganic layer in Example 3, which is 4.69 atomic %.
[0187] Similarly, in Comparative Example 1, according to Figure 5 , when the moving distance from the organic resin substrate to one direction in the thickness direction is 33.1 μm, the element concentration of Cu relative to the sum of Cu, O and inorganic elements from the inorganic layer is 98.05 atomic %, and the element concentration of inorganic elements relative to the sum of Cu and inorganic elements from the inorganic layer is 0.67 atomic %, and the above conditions are satisfied for the first time, so a copper layer near the inorganic layer is formed. That is, when the moving distance from the organic resin substrate to one direction in the thickness direction is 33.1 μm, the element concentration of O relative to the sum of Cu, O and inorganic elements from the inorganic layer is the element concentration of O in the copper layer near the inorganic layer in Comparative Example 1, which is 1.29 atomic %.
[0188] Therefore, it can be seen from Table 1 that even in the case of having an inorganic layer, Examples 1 to 3 can reduce the resistivity compared with Comparative Examples 1 and 2. In Examples 1 to 3, the element concentration of O at the copper layer 4 near the inorganic layer 3 relative to the sum of Cu, O and inorganic elements from the inorganic layer 3 is greater than 1.4 atomic % and less than 15 atomic %. In Comparative Example 1, the element concentration of O at the copper layer 4 near the inorganic layer 3 relative to the sum of Cu, O and inorganic elements from the inorganic layer 3 is less than 1.4 atomic %. In Comparative Example 2, the element concentration of O at the copper layer 4 near the inorganic layer 3 relative to the sum of Cu, O and inorganic elements from the inorganic layer 3 exceeds 15 atomic %.
[0189] Examples 1 to 3 can make the resistivity between 2.300×10 -8Specifically, it is known that the practicability of achieving a resistivity at a practical level can be ensured, especially as a conductor layer for patterning electrodes in various devices such as flat panel displays and touch panels.
[0190] [Table 1]
[0191]
[0192] It should be noted that the above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be interpreted restrictively. Modifications of the present invention that are obvious to those skilled in the art are included in the claims.
[0193] Industrial Applicability
[0194] The conductive film of the present invention is used in various devices such as flat panel displays and touch panels.
[0195] Description of Reference Numerals
[0196] 1: Conductive film; 2: Organic resin substrate; 3: Inorganic layer; 4: Copper layer.
Claims
1. A conductive film, wherein: The conductive film comprises: 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 side of the inorganic layer in the thickness direction. In the copper layer near the inorganic layer, an element concentration of O relative to the total of Cu, O, and inorganic elements derived from the inorganic layer measured by energy dispersive X-ray analysis (EDX) is 1.4 atomic % or more and 15 atomic % or less.
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.
Citation Information
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