JP6595762B2 - Conductive substrate and method for manufacturing conductive substrate - Google Patents

Description

  The present invention relates to a conductive substrate and a method for manufacturing a conductive substrate.

  A transparent conductive film for a touch panel in which an ITO (indium tin oxide) film is formed as a transparent conductive film on a polymer film has been conventionally used. (See Patent Document 1)

  By the way, in recent years, the display screen including a touch panel has been increased in screen size. Correspondingly, a conductive substrate such as a transparent conductive film for a touch panel is required to have a large area. However, since ITO has a high electric resistance value, there is a problem that it cannot cope with an increase in the area of the conductive substrate.

  For this reason, for example, as disclosed in Patent Documents 2 and 3, the use of a metal foil such as copper having excellent conductivity instead of the ITO film has been studied. However, for example, when copper is used for the wiring layer, since copper has a metallic luster, there is a problem that the visibility of the display decreases due to reflection.

  Therefore, in order to realize improvement of both the above-described characteristics of conductivity and visibility, a conductive substrate in which a blackened layer made of a black material is formed together with a wiring layer made of a metal foil such as copper is provided. It is being considered.

  However, in order to obtain a conductive substrate having a wiring pattern, it is necessary to form a desired pattern by etching the wiring layer and the blackened layer after forming the wiring layer and the blackened layer. There is a problem that the reactivity to the liquid is different between the wiring layer and the blackened layer. That is, if the wiring layer and the blackened layer are simultaneously etched, one of the layers cannot be etched into the target shape. In addition, when the wiring layer etching and the blackening layer etching are performed in separate steps, there is a problem that the number of steps increases.

JP 2003-151358 A JP 2011-018194 A JP 2013-0669261 A

  In view of the various problems of the prior art described above, an object of one aspect of the present invention is to provide a conductive substrate including a copper layer and a blackening layer that can be etched simultaneously.

In order to solve the above problems, in one aspect of the present invention,
A transparent substrate;
A copper layer formed on at least one surface of the transparent substrate;
The molybdenum content, which is formed on at least one surface side of the transparent substrate and is composed of oxygen, nitrogen, copper, nickel, and molybdenum, and the content of copper, nickel, and molybdenum is 100 atomic% There is provided a conductive substrate provided with a blackened layer having a content of 4 atomic% or more and 70 atomic% or less.

  According to one aspect of the present invention, it is possible to provide a conductive substrate including a copper layer that can be etched simultaneously and a blackening layer.

Sectional drawing of the electroconductive board | substrate which concerns on embodiment of this invention. Sectional drawing of the electroconductive board | substrate which concerns on embodiment of this invention. The top view of the electroconductive board | substrate provided with the mesh-shaped wiring which concerns on embodiment of this invention. Sectional drawing in the AA 'line of FIG. The figure which shows the wavelength dependence of the reflectance of the electroconductive board | substrate of Experimental example 2. FIG. The figure which shows the wavelength dependence of the reflectance of the electroconductive board | substrate of Experimental example 4. FIG.

Hereinafter, an embodiment of a conductive substrate and a method for manufacturing the conductive substrate of the present invention will be described.
(Conductive substrate)
The conductive substrate of this embodiment includes a transparent base material,
A copper layer formed on at least one side of the transparent substrate;
It can be set as the structure provided with the blackening layer (henceforth a "blackening layer" only) formed in the at least one surface side of a transparent base material containing oxygen, nitrogen, copper, nickel, and molybdenum. .

  The conductive substrate in this embodiment is a substrate having a copper layer or a blackened layer on the surface of a transparent substrate before patterning a copper layer or the like, and a wiring shape by patterning the copper layer or blackened layer. And a wiring board.

  First, each member included in the conductive substrate of this embodiment will be described below.

  It does not specifically limit as a transparent base material, The insulator film which permeate | transmits visible light, a glass substrate etc. can be used preferably.

  As the insulator film that transmits visible light, for example, a polyamide film, a polyethylene terephthalate film, a polyethylene naphthalate film, a resin film such as a cycloolefin film, a polycarbonate film, or the like can be preferably used.

  It does not specifically limit about the thickness of a transparent base material, It can select arbitrarily according to the intensity | strength, electrostatic capacitance, light transmittance, etc. which are required when it is set as an electroconductive board | substrate.

  Next, the copper layer will be described.

  Although it does not specifically limit also about a copper layer, In order not to reduce the transmittance | permeability of light, it is preferable not to arrange | position an adhesive agent between a copper layer and a transparent base material, or between a blackening layer. That is, the copper layer is preferably formed directly on the upper surface of another member.

  In order to directly form the copper layer on the upper surface of the other member, the copper layer preferably has a copper thin film layer. Moreover, the copper layer may have a copper thin film layer and a copper plating layer.

  For example, a copper thin film layer can be formed on a transparent substrate or a blackened layer by a dry plating method, and the copper thin film layer can be used as a copper layer. Thereby, a copper layer can be formed directly on a transparent base material or a blackening layer, without passing an adhesive agent.

  When the copper layer is thick, the copper thin film layer is used as a power feeding layer, and a copper plating layer is formed by a wet plating method to form a copper layer having a copper thin film layer and a copper plating layer. You can also. Since the copper layer has the copper thin film layer and the copper plating layer, the copper layer can be directly formed on the transparent substrate or the blackening layer without using an adhesive.

  The thickness of the copper layer is not particularly limited, and when the copper layer is used as a wiring, it can be arbitrarily selected according to the magnitude of the current supplied to the wiring, the wiring width, and the like. In particular, the thickness of the copper layer is preferably 100 nm or more, and more preferably 150 nm or more so that sufficient current can be supplied. The upper limit value of the thickness of the copper layer is not particularly limited, but if the copper layer becomes thick, side etching occurs because etching takes time when performing etching to form a wiring, and the resist peels off during the etching. Etc. are likely to occur. For this reason, the thickness of the copper layer is preferably 3 μm or less, more preferably 700 nm or less, and even more preferably 200 nm or less.

  In addition, when a copper layer has a copper thin film layer and a copper plating layer as mentioned above, it is preferable that the sum total of the thickness of a copper thin film layer and the thickness of a copper plating layer is the said range.

  Next, the blackening layer containing oxygen, nitrogen, copper, nickel and molybdenum will be described.

  Since the copper layer has a metallic luster, the copper reflects light as described above only by forming the wiring obtained by etching the copper layer on the transparent substrate. For example, when used as a conductive substrate for a touch panel, There was a problem that visibility was lowered. Therefore, a method of providing a blackened layer has been studied, but the blackened layer may not have sufficient reactivity with the etching solution, and the copper layer and the blackened layer are simultaneously etched into a desired shape. It was difficult. Therefore, the inventors of the present invention have studied, and the layer containing oxygen, nitrogen, copper, nickel and molybdenum is black, so it can be used as a blackening layer, and has sufficient reactivity with the etching solution. Thus, the inventors have found that the etching process can be performed simultaneously with the copper layer.

  The method for forming the blackening layer is not particularly limited, and can be formed by any method. However, since the blackening layer can be formed relatively easily, it is preferable to form the film by sputtering.

  The blackening layer is, for example, a sputtering method using a mixed sintering target of copper, nickel and molybdenum (hereinafter also referred to as “copper-nickel-molybdenum mixed sintering target”) while supplying oxygen and nitrogen into the chamber. Can be formed.

  Further, the blackening layer uses, for example, a copper-nickel alloy target and a molybdenum target, or a copper target and a nickel-molybdenum alloy target, and two-way simultaneous sputtering while supplying oxygen and nitrogen into the chamber. It can also be formed by the method.

  One structural example of a method for producing a copper-nickel-molybdenum mixed sintering target will be described. Since copper and molybdenum are difficult to melt and do not dissolve, it is preferable to produce a sintered body from a mixed powder of copper, nickel and molybdenum by hot pressing or hot isostatic pressing (HIP). And after processing the obtained sintered compact into a predetermined shape, it can affix on a backing plate and can be used as a target. The sintering temperature is preferably 850 ° C. or higher and 1083 ° C. or lower, more preferably 950 ° C. or higher and 1050 ° C.

  This is because the sintering does not proceed sufficiently at a temperature lower than 850 ° C., so the density of the sintered body is low, and there is a problem that cooling water may remain in the pores of the sintered body in the planar processing to be targeted. . Moreover, when it exceeds 1083 degreeC, since it exceeds melting | fusing point of copper, since copper flows out, it is unpreferable.

  In addition, the manufacturing method of the target of copper-nickel-molybdenum mixed sintering is not limited to the above manufacturing method, and is not particularly limited as long as it can be manufactured so as to be a target having a desired composition. And can be used.

  Although the supply ratio of oxygen and nitrogen supplied into the chamber at the time of sputtering is not particularly limited, oxygen is contained in the chamber at a rate of 5% by volume to 35% by volume and nitrogen at a rate of 30% by volume to 70% by volume. It is preferable to form a blackened layer while supplying.

  As described above, by setting the ratio of oxygen supply to the chamber to 5% by volume or more, the color of the blackened layer can be sufficiently black, and the function as the blackened layer can be sufficiently exhibited. preferable. The supply ratio of oxygen into the chamber is more preferably 10% by volume or more. In addition, the reactivity of the blackening layer with respect to the etching solution can be particularly increased by setting the oxygen supply amount to 35% by volume or less. When etching is performed together with the copper layer, the copper layer and the blackening layer are obtained. A desired pattern can be easily formed, which is preferable. The supply ratio of oxygen into the chamber is more preferably 20% by volume or less.

  Nitrogen can be easily etched by adding it to the atmosphere when forming the blackened layer, but if the amount added is too large, the black may become thin and the performance as a blackened layer may be reduced. is there. For this reason, the supply ratio of nitrogen during sputtering is preferably 30% by volume or more and 70% by volume or less, and more preferably 30% by volume or more and 40% by volume or less. Note that it is preferable to set the nitrogen supply ratio to 70% by volume or less because the sputtering rate of the blackened layer can be secured.

  Note that when sputtering is performed, the gas supplied into the chamber is preferably an inert gas for the remainder other than oxygen and nitrogen. For the remainder other than oxygen and nitrogen, for example, one or more gases selected from argon, xenon, neon, and helium can be supplied.

  The composition of the target used for sputtering is not particularly limited, and can be arbitrarily selected according to the composition of the blackened layer to be formed. Note that the easiness of element flight from the target during sputtering varies depending on the type of element. For this reason, the composition of a target can be selected according to the composition of the target blackening layer, and the easiness of the element in a target to fly.

  As a target used when performing sputtering, for example, a copper-nickel-molybdenum mixed sintered target can be used as described above. In this case, the composition of the target is not particularly limited as described above, but the target of the mixed sintering of copper-nickel-molybdenum preferably contains molybdenum at a ratio of 5 atomic% to 75 atomic%, and 7 atomic%. More preferably, it is contained at a ratio of 65 atomic% or less. Nickel is preferably 10 atomic percent or more and 50 atomic percent or less. In these cases, the balance can be made of copper.

The formed blackened layer can contain oxygen, nitrogen, copper, nickel, and molybdenum. The content ratio of each component in the blackened layer is not particularly limited, but the total of copper, nickel and molybdenum contained in the blackened layer, that is, the total content of metal elements is 100 atomic% a, it is preferable that the content of molybdenum is 7 0 atomic% or less than 4 atomic%.

  This is because the reflectance of light on the surface of the blackened layer can be particularly lowered by setting the molybdenum content in the metal element contained in the blackened layer to 4 atomic% or more. Further, when the content of molybdenum in the metal element is 70 atomic% or less, a conductive substrate having high etching properties and a desired pattern can be easily manufactured.

In the formed blackening layer, oxygen, nitrogen, copper, nickel and molybdenum may be contained in any form. For example, copper and molybdenum may form a mixed sintered body, and a copper-molybdenum mixed sintered body containing oxygen and / or nitrogen may be contained in the blackened layer. Further, copper, nickel or molybdenum is, for example, copper oxide (Cu ₂ O, CuO, Cu ₂ O ₃ ), copper nitride (Cu ₃ N), nickel oxide (NiO), nickel nitride (Ni ₃ N), molybdenum oxide (MoO). ₃ , MoO ₂ , Mo ₂ O ₃ ), molybdenum nitride (Mo ₂ N, MoN), and oxides or nitrides such as CuMoO ₄ , Cu ₂ MoO ₅ , and the compound is included in the blackening layer. It may be.

  The blackening layer may be a layer composed of only one kind of substance containing oxygen, nitrogen, copper, nickel and molybdenum simultaneously, such as a copper-nickel-molybdenum mixture containing oxygen and nitrogen. Good. Further, for example, the above-mentioned copper-molybdenum mixed sintered body containing oxygen and / or nitrogen, copper oxide, copper nitride, nickel oxide, nickel nitride, molybdenum oxide, molybdenum nitridation It may be a layer containing one or more kinds of substances selected from those.

  Although the thickness of a blackening layer is not specifically limited, For example, it is preferable that it is 20 nm or more, and it is more preferable to set it as 30 nm or more. The blackening layer is black as described above and functions as a blackening layer that suppresses reflection of light by the copper layer. However, when the thickness of the blackening layer is thin, sufficient blackness is obtained. In some cases, reflection of light by the copper layer cannot be sufficiently suppressed. On the other hand, since the reflection of a copper layer can be suppressed more by making the thickness of a blackening layer into the said range, it is preferable.

  The upper limit of the thickness of the blackening layer is not particularly limited, but even if it is thicker than necessary, the time required for film formation and the time required for etching when forming the wiring are increased, resulting in an increase in cost. Will be invited. For this reason, the thickness of the blackening layer is preferably 50 nm or less, and more preferably 45 nm or less.

  Further, when the sheet resistance of the blackened layer is sufficiently small, a contact portion with an electric member such as a wiring can be formed on the blackened layer, and the copper layer is exposed even when the blackened layer is located on the outermost surface. This is preferable because it is unnecessary.

Then, in order to form the contact portion of the electrical member of a circuit such as a blackening layer, the sheet resistance of the black layer is preferably 2.00 × 10 ^-1 Ω / □ or less.

  Next, a configuration example of the conductive substrate of this embodiment will be described.

  As described above, the conductive substrate of this embodiment includes a transparent base material, a copper layer, and a blackening layer containing oxygen, nitrogen, copper, nickel, and molybdenum. Under the present circumstances, the order of lamination | stacking at the time of arrange | positioning a copper layer and a blackening layer on a transparent base material is not specifically limited. Further, a plurality of copper layers and blackening layers can be formed. In order to suppress the reflection of light on the surface of the copper layer, it is preferable that the blackening layer is disposed on the surface of the copper layer on which the reflection of light is particularly desired to be suppressed. More preferably, the copper layer has a structure sandwiched between blackening layers.

  Furthermore, when a blackened layer having a low sheet resistance is included as described above, the blackened layer having a low sheet resistance is preferably disposed on the outermost surface of the conductive substrate. This is because the blackened layer having a low sheet resistance can be connected to an electric member such as a wiring, and is preferably disposed on the outermost surface of the conductive substrate so as to be easily connected.

  A specific configuration example will be described below with reference to FIGS. 1 and 2 show examples of cross-sectional views of the conductive substrate of this embodiment on a plane parallel to the lamination direction of the transparent base material, the copper layer, and the blackening layer.

  For example, as in the conductive substrate 10A shown in FIG. 1A, the copper layer 12 and the blackening layer 13 can be laminated one layer at a time on the one surface 11a side of the transparent base material 11. . Moreover, like the electroconductive board | substrate 10B shown in FIG.1 (b), copper layer 12A, 12B on the one surface 11a side of the transparent base material 11, and the other surface (other surface) 11b side, respectively. And the blackening layers 13A and 13B can be stacked one by one in that order. In addition, the order which laminates | stacks the copper layer 12 (12A, 12B) and the blackening layer 13 (13A, 13B) is not limited to the example of Fig.1 (a), (b), From the transparent base material 11 side. The blackening layer 13 (13A, 13B) and the copper layer 12 (12A, 12B) can be laminated in this order.

  Further, for example, a configuration in which a plurality of blackening layers are provided on one surface side of the transparent substrate 11 may be employed. For example, like the conductive substrate 20A shown in FIG. 2A, the first blackened layer 131, the copper layer 12, and the second blackened layer 132 are formed on the one surface 11a side of the transparent substrate 11. Can be stacked in that order.

  In this case as well, a configuration in which a copper layer, a first blackened layer, and a second blackened layer are laminated on both surfaces of the transparent substrate 11 can be adopted. Specifically, as in the conductive substrate 20B shown in FIG. 2B, the first surface 11a side of the transparent base material 11 and the other surface (the other surface) 11b side are respectively first. Blackening layers 131A and 131B, copper layers 12A and 12B, and second blackening layers 132A and 132B can be stacked in that order.

  In FIGS. 1B and 2B, when a copper layer and a blackening layer are laminated on both surfaces of the transparent base material, the transparent base material 11 serves as a symmetrical surface and the top and bottom of the transparent base material 11 are aligned. Although the example which arrange | positioned so that the laminated | stacked layer might become symmetrical was shown, it is not limited to the form which concerns. For example, in FIG. 2B, the configuration on the one surface 11a side of the transparent substrate 11 is formed by laminating the copper layer 12 and the blackening layer 13 in that order, similarly to the configuration of FIG. The layers laminated on the top and bottom of the transparent substrate 11 may be asymmetrical.

  Up to this point, the conductive substrate of the present embodiment has been described. However, in the conductive substrate of the present embodiment, the copper layer and the blackened layer are provided on the transparent base material. Reflection can be suppressed.

  The degree of light reflection of the conductive substrate of the present embodiment is not particularly limited, but for example, the conductive substrate of the present embodiment preferably has a reflectance of light having a wavelength of 550 nm of 30% or less. 20% or less is more preferable, and 10% or less is particularly preferable. This is preferable when the reflectance of light having a wavelength of 550 nm is 30% or less, for example, even when used as a conductive substrate for a touch panel, since it hardly causes a decrease in the visibility of the display.

  The reflectance can be measured by irradiating the blackened layer with light. That is, measurement can be performed from the blackened layer side of the copper layer and the blackened layer included in the conductive substrate.

  Specifically, for example, when the copper layer 12 and the blackened layer 13 are laminated in this order on one surface 11a of the transparent substrate 11 as shown in FIG. 1A, the blackened layer 13 can be irradiated with light. It can be measured from the surface side indicated by middle A.

  In addition, when the arrangement of the copper layer 12 and the blackened layer 13 is changed from that in the case of FIG. 1A and the blackened layer 13 and the copper layer 12 are laminated in this order on one surface 11a of the transparent base material 11, The reflectance can be measured from the surface 11b side of the transparent substrate 11, which is the side on which the layer 13 is located on the outermost surface.

  As will be described later, the conductive substrate can form wiring by etching the copper layer and the blackened layer, but the reflectance is arranged on the outermost surface when the transparent substrate is removed from the conductive substrate. The reflectance of the blackened layer on the surface on the light incident side is shown. For this reason, if it is before an etching process or after performing an etching process, it is preferable that the measured value in the part in which the copper layer and the blackening layer remain satisfy | fills the said range.

  As described above, the conductive substrate of this embodiment can be preferably used as a conductive substrate for a touch panel, for example. In this case, the conductive substrate can be configured to have mesh-like wiring.

  The conductive substrate provided with the mesh-like wiring can be obtained by etching the copper layer and the blackening layer of the conductive substrate of the present embodiment described so far.

  For example, a two-layer wiring can be used as a mesh wiring. A specific configuration example is shown in FIG. FIG. 3 shows a view of the conductive substrate 30 provided with mesh-like wiring as viewed from the upper surface side in the stacking direction of the copper layer and the blackened layer. The conductive substrate 30 shown in FIG. 3 has a transparent base material 11, a plurality of wirings 31A parallel to the X-axis direction in the drawing, and wirings 31B parallel to the Y-axis direction. The wirings 31A and 31B are formed by etching a copper layer, and a blackening layer (not shown) is formed on the upper surface and / or the lower surface of the wirings 31A and 31B. The blackened layer is etched in the same shape as the wirings 31A and 31B.

  The arrangement of the transparent substrate 11 and the wirings 31A and 31B is not particularly limited. An example of the arrangement of the transparent substrate 11 and the wiring is shown in FIGS. 4A and 4B correspond to cross-sectional views taken along line AA ′ of FIG.

  First, as shown to Fig.4 (a), wiring 31A, 31B may be arrange | positioned at the upper and lower surfaces of the transparent base material 11, respectively. In this case, blackening layers 32A and 32B etched in the same shape as the wiring are disposed on the upper surfaces of the wirings 31A and 31B.

  Further, as shown in FIG. 4B, a pair of transparent base materials 11A and 11B are used, and wirings 31A and 31B are arranged on the upper and lower surfaces with one transparent base material 11A interposed therebetween, and one wiring 31B may be disposed between the transparent substrate 11A and the transparent substrate 11B. Also in this case, blackened layers 32A and 32B etched in the same shape as the wiring are disposed on the upper surfaces of the wirings 31A and 31B. As described above, the arrangement of the blackened layer and the copper layer is not limited. For this reason, in any of FIGS. 4A and 4B, the arrangement of the blackening layers 32A and 32B and the wirings 31A and 31B can be reversed upside down. For example, a plurality of blackening layers can be provided.

  However, the blackening layer is preferably disposed on the surface of the copper layer surface where light reflection is particularly desired to be suppressed. For this reason, in the conductive substrate shown in FIG. 4B, for example, when it is necessary to suppress the reflection of light from the lower surface side in the figure, the positions of the blackening layers 32A and 32B, the wiring 31A, It is preferable to reverse the positions of 31B. Further, in addition to the blackening layers 32A and 32B, a blackening layer may be further provided between the wiring 31A and the transparent base material 11A and / or between the wiring 31B and the transparent base material 11B.

  The conductive substrate having the mesh-like wiring shown in FIG. 3 and FIG. 4A includes, for example, copper layers 12A and 12B on both surfaces of the transparent substrate 11 as shown in FIG. 1B and FIG. , And blackened layers 13A and 13B (131A, 132A, 131B, and 132B).

  The case where it is formed using the conductive substrate of FIG. 1B will be described as an example. First, the copper layer 12A and the blackened layer 13A on the one surface 11a side of the transparent base material 11 are shown in FIG. Etching is performed so that a plurality of linear patterns parallel to the X-axis direction are arranged at predetermined intervals. The X-axis direction in FIG. 1 (b) means a direction parallel to the width direction of each layer in FIG. 1 (b).

  A plurality of linear patterns parallel to the Y-axis direction in FIG. 1B are arranged at predetermined intervals on the copper layer 12B and the blackened layer 13B on the other surface 11b side of the transparent substrate 11. Etching is performed so that In addition, the Y-axis direction in FIG.1 (b) means the direction perpendicular | vertical to a paper surface.

  Through the above operation, the conductive substrate having the mesh-like wiring shown in FIGS. 3 and 4A can be formed. Note that the etching of both surfaces of the transparent substrate 11 can be performed simultaneously. That is, the etching of the copper layers 12A and 12B and the blackening layers 13A and 13B may be performed simultaneously.

  The conductive substrate having the mesh-like wiring shown in FIG. 3 can also be formed by using two conductive substrates shown in FIG. 1 (a) or FIG. 2 (a). The case where the conductive substrate of FIG. 1A is used will be described as an example. For the two conductive substrates shown in FIG. 1A, the copper layer 12 and the blackened layer 13 are parallel to the X-axis direction, respectively. Etching is performed so that a plurality of linear patterns are arranged at predetermined intervals. Then, the conductive substrate having mesh-like wiring is obtained by bonding the two conductive substrates so that the linear patterns formed on the respective conductive substrates intersect with each other by the etching process. be able to. The surface to be bonded when the two conductive substrates are bonded is not particularly limited. The surface A in FIG. 1A in which the copper layer 12 or the like is laminated as shown in FIG. The surface 11b in FIG. 1A on which the layer 12 and the like are not stacked may be bonded.

  In addition, it is preferable that the blackening layer is arrange | positioned in the surface which wants to suppress especially reflection of light among the copper layer surfaces. Therefore, in the conductive substrate shown in FIG. 4B, when it is necessary to suppress the reflection of light from the lower surface side in the figure, the positions of the blackening layers 32A and 32B and the wirings 31A and 31B It is preferable to arrange the positions in reverse. Further, in addition to the blackening layers 32A and 32B, a blackening layer may be further provided between the wiring 31A and the transparent base material 11A and / or between the wiring 31B and the transparent base material 11B.

  Further, for example, the surfaces 11b in FIG. 1A on which the copper layer 12 or the like of the transparent substrate 11 is not laminated may be bonded together so that the cross section has the structure shown in FIG. .

  Note that the width of the wiring and the distance between the wirings in the conductive substrate having the mesh-like wiring shown in FIGS. 3 and 4 are not particularly limited, and are selected according to, for example, the amount of current flowing through the wiring. can do.

  3 and 4 show an example in which a mesh-like wiring (wiring pattern) is formed by combining linear wirings, but the present invention is not limited to such a configuration, and a wiring pattern is configured. The wiring can have any shape. For example, the shape of the wiring constituting the mesh-like wiring pattern can be changed to various shapes such as jagged lines (zigzag straight lines) so that moire (interference fringes) does not occur between the images on the display.

Thus, a conductive substrate having a mesh-like wiring composed of two layers of wiring can be preferably used as a conductive substrate for a projected capacitive touch panel, for example.
(Method for producing conductive substrate)
Next, a configuration example of the method for manufacturing the conductive substrate according to the present embodiment will be described.

The manufacturing method of the conductive substrate of this embodiment is as follows:
A transparent substrate preparation step of preparing a transparent substrate;
A copper layer forming step of forming a copper layer on at least one surface side of the transparent substrate;
It is preferable to have a blackened layer forming step of forming a blackened layer containing oxygen, nitrogen, copper, nickel and molybdenum on at least one surface side of the transparent substrate.

  Although the manufacturing method of the electroconductive board | substrate of this embodiment is demonstrated below, since it can be set as the structure similar to the case of the above-mentioned electroconductive board | substrate except the point demonstrated below, description is abbreviate | omitted.

  As described above, in the conductive substrate of this embodiment, the order of stacking when the copper layer and the blackened layer are arranged on the transparent substrate is not particularly limited. Further, a plurality of copper layers and blackening layers can be formed. For this reason, the order of the copper layer forming step and the blackened layer forming step and the number of times of execution are not particularly limited, and are performed at an arbitrary number of times according to the structure of the conductive substrate to be formed. be able to.

  The step of preparing the transparent base material is a step of preparing a transparent base material made of, for example, an insulating film that transmits visible light, a glass substrate, or the like, and the specific operation is not particularly limited. For example, in order to use for each process in a latter process, it can cut | disconnect etc. to arbitrary sizes as needed.

  In addition, since it has already stated about the film which can be used especially suitably as an insulator film which permeate | transmits visible light, description is abbreviate | omitted here.

  Next, the copper layer forming step will be described.

  As described above, the copper layer preferably has a copper thin film layer. Moreover, it can also have a copper thin film layer and a copper plating layer. For this reason, a copper layer formation process can have a process of forming a copper thin film layer, for example with a dry plating method. Moreover, the copper layer forming step may include a step of forming a copper thin film layer by a dry plating method and a step of forming a copper plating layer by a wet plating method using the copper thin film layer as a power feeding layer. .

  The dry plating method used for forming the copper thin film layer is not particularly limited, and for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like can be used. In particular, as the dry plating method used for forming the copper thin film layer, it is more preferable to use the sputtering method because the film thickness can be easily controlled.

  The process of forming a copper thin film layer will be described taking the case of using a winding type sputtering apparatus as an example. First, a copper target is mounted on a sputtering cathode, and a base material, specifically, a transparent base material on which a transparent base material or a blackened layer is formed is set in a vacuum chamber. After evacuating the inside of the vacuum chamber, Ar gas is introduced to maintain the inside of the apparatus at about 0.13 Pa to 1.3 Pa. In this state, while conveying the substrate from the unwinding roll at a speed of, for example, about 1 to 20 m per minute, power is supplied from the DC power supply for sputtering connected to the cathode, and sputtering discharge is performed, and the desired material is applied on the substrate. The copper thin film layer can be continuously formed.

  The conditions in the step of forming the copper plating layer by the wet plating method, that is, the conditions for the electroplating treatment are not particularly limited, and various conditions according to ordinary methods may be adopted. For example, a copper plating layer can be formed by supplying a base material on which a copper thin film layer is formed in a plating tank containing a copper plating solution and controlling the current density and the conveyance speed of the base material.

  Next, the blackening layer forming process will be described.

  Although the blackening layer forming step is not particularly limited, as described above, the blackening layer can be formed by sputtering.

  At this time, a copper-nickel-molybdenum mixed sintered target can be used as the target.

  Further, as described above, a film can also be formed by a binary simultaneous sputtering method using a copper-nickel alloy target and a molybdenum target, or using a copper target and a nickel-molybdenum alloy target.

  The composition of the target used for sputtering is not particularly limited, and can be arbitrarily selected according to the composition of the blackened layer to be formed. Note that the easiness of element flight from the target during sputtering varies depending on the type of element. For this reason, the composition of a target can be selected according to the composition of the target blackening layer, and the easiness of the element in a target to fly.

  For example, a copper-nickel-molybdenum mixed sintering target preferably contains molybdenum in a proportion of 5 atomic% to 75 atomic% and nickel in a ratio of 10 atomic% to 50 atomic%. Moreover, it is more preferable to contain molybdenum at a ratio of 7 atomic% to 65 atomic%. The remainder can be made of copper.

  Further, it is preferable to form the blackened layer by sputtering while supplying oxygen in the chamber at a rate of 5% by volume to 35% by volume and nitrogen at a rate of 30% by volume to 70% by volume.

  In particular, the supply ratio of oxygen into the chamber is more preferably 10% by volume or more and 20% by volume or less. Further, the supply ratio of nitrogen into the chamber is more preferably 30% by volume to 40% by volume.

  Note that when sputtering is performed, the gas supplied into the chamber is preferably an inert gas for the remainder other than oxygen and nitrogen. For the remainder other than oxygen and nitrogen, for example, one or more selected from argon, xenon, neon, and helium can be supplied.

  And as for the electroconductive board | substrate obtained by the manufacturing method of the electroconductive board | substrate demonstrated here, it is preferable that the copper layer is 100 nm or more like the conductive board | substrate mentioned above, and it shall be 150 nm or more. More preferred. The upper limit value of the thickness of the copper layer is not particularly limited, but is preferably 3 μm or less, more preferably 700 nm or less, and further preferably 200 nm or less.

  Also in the conductive substrate obtained by the conductive substrate manufacturing method described here, the thickness of the blackening layer is not particularly limited, but is preferably 20 nm or more, for example, 30 nm or more. It is more preferable. The upper limit of the thickness of the blackening layer is not particularly limited, but is preferably 50 nm or less, and more preferably 45 nm or less.

  The formed blackening layer can contain oxygen, nitrogen, copper, nickel and molybdenum. The content ratio of each component in the blackened layer is not particularly limited, but when the total of copper, nickel and molybdenum, which are metal elements contained in the blackened layer, is 100 atomic%, the content of molybdenum Is preferably 4 atom% or more and 70 atom% or less. This is because the reflectance of light on the surface of the blackened layer can be particularly lowered by setting the molybdenum content in the metal element contained in the blackened layer to 4 atomic% or more. Further, when the content of molybdenum in the metal element is 70 atomic% or less, a conductive substrate having high etching properties and a desired pattern can be easily manufactured.

In the formed blackening layer, oxygen, nitrogen, copper, nickel, and molybdenum may be contained in any form. For example, copper and molybdenum may form a mixed sintered body, and a copper-molybdenum mixed sintered body containing oxygen and / or nitrogen may be contained in the blackened layer. Further, copper or molybdenum is, for example, copper oxide (Cu ₂ O, CuO, Cu ₂ O ₃ ), copper nitride (Cu ₃ N), nickel oxide (NiO), nickel nitride (Ni ₃ N), molybdenum oxide (MoO ₃ , MoO ₂ , Mo ₂ O ₃ ), molybdenum nitride (Mo ₂ N, MoN), and further oxides or nitrides such as CuMoO ₄ , Cu ₂ MoO ₅ are generated, and the compound is included in the blackening layer. Also good.

  The blackening layer may be a layer composed of only one kind of substance containing oxygen, nitrogen, copper, nickel and molybdenum simultaneously, such as a copper-nickel-molybdenum mixture containing oxygen and nitrogen. Good. Further, for example, the above-mentioned copper-molybdenum mixed sintered body containing oxygen and / or nitrogen, copper oxide, copper nitride, nickel oxide, nickel nitride, molybdenum oxide, molybdenum nitridation It may be a layer containing one or more kinds of substances selected from those.

  When the formed blackened layer has a sufficiently low sheet resistance, a contact portion with an electric member such as a wiring can be formed on the blackened layer, and the copper layer is formed even when the blackened layer is located on the outermost surface. This is preferable because it is not necessary to expose.

Then, in order to form the contact portion of the electrical member of a circuit such as a blackening layer, the sheet resistance of the black layer is preferably 2.00 × 10 ^-1 Ω / □ or less.

  And the conductive substrate obtained by the manufacturing method of the conductive substrate demonstrated here can be made into the conductive substrate provided with the mesh-shaped wiring. In this case, in addition to the above-described steps, an etching step of forming a wiring by etching the copper layer and the blackening layer can be further included.

  In the etching step, for example, first, a resist having an opening corresponding to a portion to be removed by etching is formed on the outermost surface of the conductive substrate. In the case of the conductive substrate shown in FIG. 1A, a resist can be formed on the exposed surface A of the blackening layer 13 disposed on the conductive substrate. Note that a method for forming a resist having an opening corresponding to a portion to be removed by etching is not particularly limited. For example, the resist can be formed by a photolithography method.

  Next, the copper layer 12 and the blackened layer 13 can be etched by supplying an etching solution from the upper surface of the resist.

  In addition, when a copper layer and a blackening layer are disposed on both surfaces of the transparent substrate 11 as shown in FIG. 1B, a resist having openings of predetermined shapes on the outermost surfaces A and B of the conductive substrate. The copper layer and the blackened layer formed on both surfaces of the transparent substrate 11 may be etched simultaneously.

  In addition, the copper layer and the blackened layer formed on both sides of the transparent substrate 11 can be etched on one side. That is, for example, after the copper layer 12A and the blackened layer 13A are etched, the copper layer 12B and the blackened layer 13B can be etched.

  Since the blackening layer exhibits the same reactivity to the etching solution as the copper layer, the etching solution used in the etching step is not particularly limited, and an etching solution generally used for etching the copper layer is preferably used. be able to. As the etching solution, for example, a mixed aqueous solution of ferric chloride and hydrochloric acid can be used more preferably. The contents of ferric chloride and hydrochloric acid in the etching solution are not particularly limited. For example, ferric chloride is preferably contained in a proportion of 5% by mass to 50% by mass, and 10% by mass. More preferably, it is contained at a ratio of 30% by mass or less. Further, for example, the etching solution preferably contains hydrochloric acid in a proportion of 1% by mass or more and 50% by mass or less, and more preferably contains 1% by mass or more and 20% by mass or less. The remainder can be water.

  Although the etching solution can be used at room temperature, it is preferably heated to increase the reactivity. For example, it is preferably heated to 40 to 50 ° C.

  The specific form of the mesh-like wiring obtained by the above-described etching process is as described above, and the description thereof is omitted here.

  In addition, as described above, two conductive substrates having a copper layer and a blackened layer are bonded to one side of the transparent base material 11 shown in FIGS. 1A and 2A and meshed. In the case where the conductive substrate is provided with a conductive wiring, a step of bonding the conductive substrate can be further provided. At this time, a method for bonding the two conductive substrates is not particularly limited, and the bonding can be performed using, for example, an adhesive.

  The conductive substrate and the method for manufacturing the conductive substrate of the present embodiment have been described above. According to such a conductive substrate, since the copper layer and the blackened layer show substantially the same reactivity with the etching solution, a desired wiring can be easily formed. Further, since the blackened layer is black, reflection of light by the copper layer can be suppressed, and for example, when a conductive substrate for a touch panel is used, a reduction in visibility can be suppressed.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited to these Examples.

First, the evaluation method of the sample produced in each experiment example mentioned later is demonstrated.
(Evaluation methods)
(1) Optical characteristics (reflectance, brightness)
Optical characteristics (reflectance) of the conductive substrates prepared in Experimental Examples 2 and 4 below were measured. Further, the brightness was calculated from the measured optical characteristics (reflectance).

  The measurement was performed by installing a reflectance measurement unit in an ultraviolet-visible spectrophotometer (manufactured by Hitachi High-Technologies Corporation: U-4000).

  In Experimental Examples 2 and 4 below, conductive substrates having a cross-sectional shape similar to that shown in FIG. Therefore, with respect to the outermost surface A in FIG. 1A on the side where the copper layer and blackening layer of the produced conductive substrate are formed, the incident angle is 5 ° and the light receiving angle is 5 °, and the wavelength range is 350 nm or more and 780 nm or less. The reflectance when irradiated with the light of was measured. In the measurement, light having a wavelength changed every 1 nm in a wavelength range of 350 nm to 780 nm is irradiated, and the reflectance for each wavelength is measured.

  In the measurement, in order to correct the warp of the PET film, the samples of each experimental example and comparative example were placed on a glass substrate and fixed with a clamp, and the measurement was performed by irradiating light from the blackened layer side.

Using the measured reflectance, coordinates in the CIE 1976 (L ^* ) color space were calculated using a color calculation program based on JIS Z8781-4: 2013 under the condition of the light source A field of view of 2 degrees.
(2) Dissolution test The sample which formed in the following Experimental examples 1 and 3 and which formed the blackening layer on the transparent base material was immersed in etching liquid, and the dissolution test of the blackening layer was done. In Experimental Example 1-4-1 to Experimental Example 1-4-3, a molybdenum oxynitride film is formed instead of the blackened layer. Therefore, in Experimental Example 1-4-1 to Experimental Example 1-4-3, the dissolution test of the formed molybdenum oxynitride film is performed.

  As an etching solution, an aqueous solution containing 10% by mass of ferric chloride and 10% by mass of hydrochloric acid used as an etching solution for the copper layer and the balance consisting of water is used, and the temperature of the etching solution is room temperature (25 ° C.). Carried out.

  Next, a method for evaluating the dissolution test will be described.

  In order to prescribe the evaluation of the dissolution test, the entire surface on one surface of a polyethylene terephthalate resin (PET resin) having a length of 5 cm, a width of 5 cm, and a thickness of 0.05 mm, which is the transparent substrate used in Experimental Examples 1 and 3, A preliminary experiment was conducted in which a sample on which a copper layer having a thickness of 300 nm was formed was immersed in an etching solution. In this case, it was confirmed that the copper layer was dissolved within 10 seconds.

For this reason, the case where the entire blackened layer was dissolved within 10 seconds after immersion in the etching solution was marked with ◎, the case where the entire blackened layer was dissolved within 30 seconds, and the whole blackened layer dissolved within 1 minute. The case where the blackened layer was completely dissolved within 3 minutes was evaluated as Δ, and the case where the blackened layer was not completely dissolved even after 3 minutes was left as x.
(3) EDS analysis About the sample which produced in Experiment example 1 and 3 and formed the blackening layer on the transparent base material, SEM-EDS apparatus (SEM: JEOL Co., Ltd. make: JSM-7001F, EDS: Thermo Fisher Scientific Co., Ltd. Model: Detector UltraDry analysis system ERAN analysis was performed using NORAN System 7).
(4) Sheet resistance About the sample which produced in Experimental Examples 1 and 3 and formed the blackening layer on the transparent base material, the sheet resistance of the blackening layer was evaluated.

Sheet resistance was measured using a four-probe method. In the four-probe method, four needle-shaped electrodes are arranged on the same line on the surface of the sample to be measured, a constant current is passed between the two outer probes, and the potential difference between the two inner probes is measured. This is a method of measuring resistance. The measurement was performed using a four-point probe measuring instrument (Mitsubishi Chemical Co., Ltd. model: Loresta IP).
(Sample preparation conditions)
The sample manufacturing conditions and the evaluation results in each experimental example will be described below.
[Experimental Example 1]
In Experimental Example 1, 12 samples of Experimental Example 1-1-1 to Experimental Example 1-4-3 shown below were prepared, and EDS analysis, dissolution test, and sheet resistance evaluation for the composition of the blackened layer Carried out.

In addition, this experiment example was implemented as a preliminary experiment for the experiment example 2 mentioned later, and becomes a reference example.
(Experimental Example 1-1-1 to Experimental Example 1-3-3)
Samples (Experimental Example 1-1-1 to Experimental Example 1-3-3) in which a blackening layer containing oxygen, nitrogen, copper, nickel, and molybdenum was formed on a PET substrate that was a transparent base material were prepared. . A specific procedure will be described below.
In addition, Experimental Example 1-1-1 to Experimental Example 1-1-3, Experimental Example 1-2-1 to Experimental Example 1-2-3, Experimental Example 1-3-1 to Experimental Example 1-3-3 When the samples are collectively shown, they may be simply referred to as Experimental Example 1-1-1 to Experimental Example 1-3-3 as described above.

  First, a transparent substrate made of polyethylene terephthalate resin (PET, trade name “Lumirror U48”, manufactured by Toray Industries, Inc.) having a length of 5 cm, a width of 5 cm, and a thickness of 0.05 mm was prepared.

  Next, a blackening layer was formed by direct current sputtering.

  The blackening layer 13 was formed using a sputtering apparatus (Model: SIH-450 manufactured by ULVAC, Inc.).

  Specific conditions and procedures for sputtering when forming the blackening layer will be described below.

  First, as a target for forming the blackened layer, a two-target of a molybdenum target and a copper-40 at% nickel alloy target was used. The copper-40 at% nickel alloy target means an alloy target composed of 40 at% nickel and the balance copper.

  In addition, when the blackening layer is formed by sputtering, a total of 10 SCCM of mixed gas (nitrogen and oxygen) in which the volume ratio of nitrogen and oxygen is 4: 1 and the argon gas are contained in the chamber. While feeding.

  Specifically, the ratio (Ar gas: mixed gas) between the argon gas supplied into the chamber and the mixed gas (nitrogen and oxygen) is 5: 5 (condition 1), 3: 7 (condition 2), 2 : Sputtering was performed while changing the ratio to 8 (Condition 3) and supplying each volume% of oxygen, nitrogen, and argon at the ratios shown in Table 1. The conditions of the gas ratio supplied into the chamber shown in Table 1 are hereinafter referred to as Condition 1 to Condition 3.

黒化層を成膜する際の具体的な手順について説明する。

A specific procedure for forming the blackening layer will be described.

First, the prepared transparent base material was set on a substrate holder, and the inside of the chamber was evacuated. In addition, the ultimate vacuum in the chamber before sputtering was 1.5 × 10 ⁻⁴ Pa.

  And about each experiment example, argon gas and the mixed gas were supplied in the chamber so that the conditions of Table 1 and the above-mentioned gas might be satisfied. The substrate holder was rotated at a speed of 30 rpm.

  Then, DC power calculated in advance so that the metal ratio of copper-nickel and molybdenum supplied from the target is three conditions of 65:35, 50:50, and 25:75 is applied to each target, and binary A blackened layer (film thickness 300 nm) was produced by co-sputtering.

  In addition, the magnitude | size of DC electric power for making the metal ratio of the copper-nickel alloy supplied from a copper-40at% nickel alloy target and a molybdenum target and molybdenum into a desired value was calculated by the following preliminary tests. did.

  A copper-nickel alloy film and a molybdenum film were formed on a glass plate with gas conditions 1 to 3, DC power 400 W, and sputtering time 20 minutes, respectively, and the film thickness was measured to form a film formation rate (Vai: nm / (W · min), a = Cu—Ni, Mo, i = 1, 2, 3). Note that i means a gas condition number.

  From this, the DC power (Pai) applied to each target was calculated from the following formula, assuming that the metal ratio of the target composition of copper-nickel alloy and molybdenum was m: n, the film thickness was 300 nm, and the sputtering time was 20 minutes.

As described above, a copper-40 at% nickel alloy is used as the copper-nickel alloy. For this reason, the specific target composition of copper and nickel is calculated as 40% of the metal ratio m of the target composition as nickel and the balance as copper.
P _Cu-Nii = 300 × m / (m + n) / (20 * V _Cu-Nii )
P _Moi = 300 × n / (m + n) / (20 * V _Moi )

  As described so far, the three conditions for the metal ratio of the metal supplied from the copper-nickel alloy target and the molybdenum target and the three conditions for the gas ratio supplied into the chamber are changed, and the conditions are changed. Nine types of combined films were formed on a transparent substrate. At this time, samples in which nine types of films were formed on a transparent substrate were referred to as Experimental Example 1-1-1 to Experimental Example 1-3-3.

Table 2 summarizes the conditions for producing the nine types of films and the numbers of the experimental examples. For example, in Experimental Example 1-1-1, the gas ratio (volume%) of oxygen, nitrogen, and argon supplied into the chamber is condition 1 (O ₂ : N ₂ : Ar = 10: 40: 50), and copper − DC power is applied so that the metal ratio (Cu: Ni: Mo, each at%) of the metal supplied from the nickel and molybdenum target is 39:26:35.
(Experimental example 1-4-1 to Experimental example 1-4-3)
As shown in Table 2, as a comparative sample, except that only a molybdenum target was used as a target, the same procedure as in Experimental Example 1-1-1 to Experimental Example 1-1-3 was performed. A sample on which an oxynitride film was formed was also produced. Hereinafter, these comparative samples are referred to as Experimental Example 1-4-1 to Experimental Example 1-4-3.

Below, the evaluation result of the produced sample is demonstrated.
(Evaluation of composition of blackened layer: EDS analysis result)
From the EDS analysis, it was confirmed that all of the blackened layers of Experimental Example 1-1-1 to Experimental Example 1-3-3 were composed of copper, nickel, molybdenum, nitrogen, and oxygen.

  Some measurement results are shown in Table 3.

(Dissolution test results)
A dissolution test was performed at 25 ° C. using an aqueous solution containing 10% by mass of ferric chloride, 10% by mass of hydrochloric acid, and the balance water as an etching solution. The results are shown in Table 4.

  According to the results shown in Table 4, it was confirmed that the blackened layer was dissolved within 30 seconds in any sample of Experimental Example 1-1-1 to Experimental Example 1-3-3. That is, it was confirmed that the blackened layer of these experimental examples showed the same solubility as the copper layer.

  From the above results, when the blackened layer produced in Experimental Example 1-1-1 to Experimental Example 1-3-3 was formed on the copper layer and patterned, the copper layer and the blackened layer were simultaneously formed. It was confirmed that the etching process was possible. For this reason, it has confirmed that all the electroconductive board | substrates produced in Experimental example 2 mentioned later are the electroconductive board | substrates provided with the copper layer and blackening layer which can perform an etching process simultaneously.

Samples of Experimental Example 1-4-1 to Experimental Example 1-4-3 in which a molybdenum oxynitride film is formed instead of the blackening layer containing oxygen, nitrogen, copper, nickel, and molybdenum are shown in Table 4. As shown, it was confirmed that it took longer than 30 seconds for the blackened layer to dissolve except in the case of Experimental Example 1-4-3.
(Evaluation of sheet resistance)
The sheet resistance of the blackened layer was evaluated for the samples of each experimental example. The results are shown in Table 5. The unit of numerical values in the table is Ω / □. Moreover, the same experiment number is used about the sample produced on the same conditions except the film thickness of the blackening layer.

表５から実験例１−１−１〜実験例１−３−３のいずれの試料についてもシート抵抗は０．２Ω／□未満であり、十分小さいことが確認できた。

From Table 5, it was confirmed that the sheet resistance was less than 0.2Ω / □ for all the samples of Experimental Example 1-1-1 to Experimental Example 1-3-3, which was sufficiently small.

[Experimental example 2]
Next, a conductive substrate was produced with reference to the result of the preliminary experiment conducted in Experimental Example 1, and the evaluation was performed.

  In this experimental example, a conductive substrate having a structure in which a copper layer and a blackened layer are formed on one surface of a transparent substrate, or a conductive substrate in which a molybdenum oxynitride film is formed instead of the blackened layer is used. Produced. As the conductive substrate, nine types of samples having different film formation conditions for the blackened layer and one type of sample in which a molybdenum oxynitride film was formed instead of the blackened layer were prepared.

  Experimental example 2-1-1 to Experimental example 2-1-3, Experimental example 2-2-1 to Experimental example 2-2-3, Experimental example 2-3-1 to Experimental example 2-3 described below 3 is an example, and experimental example 2-4-1 is a comparative example.

In addition, Experimental Example 2-1-1 to Experimental Example 2-1-3, Experimental Example 2-2-1 to Experimental Example 2-2-3, Experimental Example 2-3-1 to Experimental Example 2-3-3 When collectively shown, it may be simply referred to as Experimental Example 2-1-1 to Experimental Example 2-3-3.
(Experimental example 2-1-1 to Experimental example 2-3-3)
As Experimental Example 2-1-1 to Experimental Example 2-3-3, a conductive substrate having a blackening layer formed under the nine conditions shown in Table 6 and having the structure shown in FIG. That is, a conductive substrate having a structure in which a copper layer and a blackening layer were formed on one side of a transparent substrate was prepared.

In the case of Experimental Example 2-1-1, the gas ratio (volume%) of oxygen, nitrogen, and argon supplied into the chamber is Condition 1 (O ₂ : N ₂ : Ar = 10: 40: 50). Further, the black layer was formed by applying DC power so that the metal ratio (at%) of the metal supplied from the copper-nickel target and the molybdenum target was 39:26:35 Cu: Ni: Mo. It is filming.

  Also, among the experimental examples of Experimental Example 2, for the experimental example in which the number after Experimental Example 2- of the experimental number is the same as Experimental Example 1, the blackened layer is formed under the same conditions except for the film thickness It is shown that. For example, in Experimental Example 2-1-1 and Experimental Example 1-1-1, the blackening layer is formed under the same conditions except for the film thickness.

  Further, as Experimental Example 2-4-1, except that the copper-nickel target was not used and only the molybdenum target was used, and a molybdenum oxynitride film was formed instead of the blackening layer, Experimental Example 2-1 In the same manner as in Example 1, a conductive substrate was produced.

  Hereinafter, a procedure for producing the conductive substrate will be described in detail in Experimental Example 2-1-1 to Experimental Example 2-3-3.

  First, a transparent substrate 11 made of polyethylene terephthalate resin (PET, trade name “Lumirror U48”, manufactured by Toray Industries, Inc.) having a length of 5 cm, a width of 5 cm, and a thickness of 0.05 mm was prepared.

  Next, a copper layer 12 was formed on the entire surface of one surface of the transparent substrate 11. The copper layer 12 formed a copper thin film layer by a sputtering method, and then formed a copper plating layer by a wet plating method using the copper thin film layer as a power feeding layer. Specifically, a copper thin film layer having a thickness of 100 nm was first formed on one surface of the transparent substrate 11 by a direct current sputtering method using a Cu target (manufactured by Sumitomo Metal Mining Co., Ltd.). Thereafter, a copper plating layer was laminated by 0.5 μm by electroplating to form a copper layer 12.

  Next, a blackened layer 13 was formed on the entire surface of the copper layer 12 by the binary simultaneous sputtering method in the same manner as in Experimental Example 1.

A blackening layer 13 having a thickness of 30 nm was formed in each experimental example by the sputtering method.
(Experimental example 2-4-1)
For Experimental Example 2-4-1, a conductive substrate was produced in the same manner as Experimental Example 2-1-1 except that only a molybdenum target was used without using a copper-nickel target.

The evaluation result of the conductive substrate obtained by the above steps will be described.
(Optical characteristics: reflectance evaluation)
Among the produced conductive substrates, Experimental Example 2-1-1, Experimental Example 2-2-1, Experimental Example 2-2-2, Experimental Example 2-3-1, Experimental Example 2-3-2, Experimental Example The reflectance measurement was performed on 2-4-1. The wavelength dependence of the reflectance is shown in FIG.

  From the results shown in FIG. 5, it was confirmed that the reflectivity for light having a wavelength of 550 nm was lower than 30% in any of the experimental examples. Further, Experimental Example 2-2-2 (copper / nickel / molybdenum metal ratio = 30: 20: 50, gas condition 2) Experimental example 2-3-2 (copper / nickel / molybdenum metal ratio = 15: 10: 75, gas) Condition 2) shows that the reflectance at a wavelength of 550 nm is close to 0, and the reflectance is less than 20% for light in the wavelength range of 350 nm to 550 nm.

Table 7 shows the value of brightness L ^* calculated from the reflectance measured for the conductive substrate of each experimental example. In any of the experimental examples shown in Table 7, the lightness L ^* was 55 or less, and it was confirmed that the characteristics were good.

実験例２−１−１〜実験例２−３−３においては、上述のように実験例１−１−１〜実験例１−３−３と同様の条件で黒化層を形成している。このため、実験例２−１−１〜実験例２−３−３で作製した導電性基板に含まれる黒化層は、実験例１−１−１〜実験例１−３−３で評価を行った黒化層と同様の特性を有するものといえる。すなわち、実験例２−１−１〜実験例２−３−３で作製した導電性基板に形成した黒化層の組成や、シート抵抗は、実験例１で評価した対応する実験例１−１−１〜実験例１−３−３と同様の特性となっている。

In Experimental Example 2-1-1 to Experimental Example 2-3-3, the blackening layer is formed under the same conditions as in Experimental Example 1-1-1 to Experimental Example 1-3-3 as described above. . For this reason, the blackening layer contained in the conductive substrate produced in Experimental Example 2-1-1 to Experimental Example 2-3-3 was evaluated in Experimental Example 1-1-1 to Experimental Example 1-3-3. It can be said that it has the same characteristics as the blackened layer. That is, the composition and the sheet resistance of the blackening layer formed on the conductive substrate prepared in Experimental Example 2-1-1 to Experimental Example 2-3-3 are the same as the corresponding Experimental Example 1-1 evaluated in Experimental Example 1. The characteristics are the same as those of -1 to Experimental Example 1-3-3.

  Further, as described in Experimental Example 1, the blackened layer evaluated in Experimental Example 1-1-1 to Experimental Example 1-3-3 shows the same solubility as the copper layer in the etching solution in the dissolution test. I was able to confirm. From this, the conductive substrates produced in Experimental Example 2-1-1 to Experimental Example 2-3-3 were each provided with a copper layer that could be etched simultaneously and a blackening layer. It can be said that it is a conductive substrate.

[Experiment 3]
In Experimental Example 3, a copper-nickel-molybdenum mixed sintering target was prepared, and using this target, Experimental Example 3-3-1 to Experimental Example 3-3-3 and Experimental Example 3-4- 1 to 6 samples of Experimental Example 3-4-3 were prepared.

  In addition, in the case where Experimental Example 3-3-1 to Experimental Example 3-3-3 and Experimental Example 3-4-1 to Experimental Example 3-4-3 are collectively shown, Experimental Example 3-3-1 to Experiment It may be described as Example 3-4-3.

  And the EDS analysis about the composition of a blackening layer, the dissolution test, and sheet resistance evaluation were implemented.

In addition, this experiment example was implemented as a preliminary experiment for the experiment example 4 mentioned later, and becomes a reference example.
(Copper-nickel-molybdenum mixed sintering target: Experimental example 3-1 to Experimental example 3-5)
In this experimental example, first, copper-nickel-molybdenum mixed sintering targets of Experimental example 3-1 to Experimental example 3-5 were prepared. The specific procedure is shown below.

  As a starting material powder, Mo powder (manufactured by Nippon Steel, secondary particle diameter of about 200 to 500 μm), Ni powder (manufactured by 3N NIE08PB 63 μm) and Cu powder (3N CUE13PB <43 μm by high purity chemical) are predetermined amounts. Weigh and mix in mortar. At this time, the starting material powders were weighed and mixed so that the mixing ratio of the starting material powders in each experimental example was a value shown in Table 8.

Subsequently, the obtained mixed powder was put into a graphite mold having an inner diameter of 3 inches and sintered by a hot press method, and five types of sintered bodies of Experimental Examples 3-1 to 3-5 having different compositions were produced. The surface pressure during sintering by the hot press method was 136 kg weight / cm ² , the hot press temperature (HP temperature) was 900 ° C. or 1000 ° C. shown in the table, and the holding time was 1 hour. As shown in Table 8, the density of the obtained sintered body was 82% to 93%, and it was confirmed that it could be used as a sputtering target.

（実験例３−３−１〜実験例３−４−１）
作製した銅−ニッケル−モリブデン混合焼結ターゲット（以下、単に「焼結ターゲット」とも記載する）の組成と成膜される黒化層の組成との関係を確認するために、実験例３−３、実験例３−４で作製したターゲットを用いて、実験例１と同様の試料を作製した。なお、実験例３−３−１〜実験例３−３−３は表８中実験例３−３として示したターゲットを用いて黒化層を成膜している。また、実験例３−４−１〜実験例３−４−３は表８中実験例３−４として示したターゲットを用いて黒化層を成膜している。

(Experimental Example 3-3-1 to Experimental Example 3-4-1)
In order to confirm the relationship between the composition of the produced copper-nickel-molybdenum mixed sintered target (hereinafter also simply referred to as “sintered target”) and the composition of the blackened layer to be formed, Experimental Example 3-3 Using the target prepared in Experimental Example 3-4, a sample similar to Experimental Example 1 was manufactured. In Experimental Example 3-3-1 to Experimental Example 3-3-3, a blackened layer was formed using the target shown as Experimental Example 3-3 in Table 8. In Experimental Example 3-4-1 to Experimental Example 3-4-3, a blackened layer was formed using the target shown as Experimental Example 3-4 in Table 8.

  The conditions and procedure for producing the sample will be described below.

  First, a transparent substrate made of polyethylene terephthalate resin (PET, trade name “Lumirror U48”, manufactured by Toray Industries, Inc.) having a length of 5 cm, a width of 5 cm, and a thickness of 0.05 mm was prepared.

  Next, a blackening layer was formed by direct current sputtering.

  The blackening layer was formed using a sputtering apparatus (Model: SIH-450, manufactured by ULVAC, Inc.).

  A specific procedure for forming the blackening layer will be described.

First, the prepared transparent base material was set on a substrate holder, and the inside of the chamber was evacuated. In addition, the ultimate vacuum in the chamber before sputtering was 1.5 × 10 ⁻⁴ Pa.

  Next, argon gas and a mixed gas (mixed gas of oxygen and nitrogen) were supplied into the chamber so as to satisfy the gas ratio conditions of Table 9 for each experimental example. The substrate holder was rotated at a speed of 30 rpm.

  And DC power was applied to the target, and the blackening layer (film thickness of 300 nm) was produced.

  About the obtained sample, the composition of the blackening layer was analyzed by EDS. The results are shown in Table 9.

また、作製した試料について実験例１の場合と同様にして溶解試験、及びシート抵抗の評価を実施した。結果を表１０に示す。

In addition, the dissolution test and the sheet resistance evaluation were performed on the prepared samples in the same manner as in Experimental Example 1. The results are shown in Table 10.

  In Table 10, the results of the dissolution test are shown as etching properties.

溶解試験についてはいずれの試料においても評価結果が二重丸となっており、いずれの試料においても１０秒以内に黒化層が溶解していることが確認できた。すなわち、これらの実験例の黒化層は、銅層と同等の溶解性を示すことが確認できた。

Regarding the dissolution test, the evaluation results were double circles in any sample, and it was confirmed that the blackened layer was dissolved within 10 seconds in any sample. That is, it was confirmed that the blackened layer of these experimental examples showed the same solubility as the copper layer.

Furthermore, it was confirmed that the sheet resistance was sufficiently small as less than 2.0 × 10 ⁻¹ Ω / □ in any sample.
[Experimental Example 4]
Next, a conductive substrate was prepared with reference to the result of the preliminary experiment performed in Experimental Example 3, and the evaluation was performed.

  In this experimental example, as in the case of Experimental example 2, the conductive structure having the structure shown in FIG. 1A and having a structure in which a copper layer and a blackening layer are formed on one surface of the transparent substrate. A conductive substrate was produced. As the conductive substrate, six types of samples having different film forming conditions for the blackened layer were prepared.

  Experimental Example 4-3-1 to Experimental Example 4-3-3 and Experimental Example 4-4-1 to Experimental Example 4-4-3 described below are examples.

  In addition, in the case where Experimental Example 4-3-1 to Experimental Example 4-3-3 and Experimental Example 4-4-1 to Experimental Example 4-4-3 are collectively shown, Experimental Example 4-3-1 to Experimental It may be described as Example 4-4-3.

  The procedure for producing the conductive substrate will be described in detail below.

  First, a transparent substrate 11 made of polyethylene terephthalate resin (PET, trade name “Lumirror U48”, manufactured by Toray Industries, Inc.) having a length of 5 cm, a width of 5 cm, and a thickness of 0.05 mm was prepared.

  Next, a copper layer 12 was formed on the entire surface of one surface of the transparent substrate 11. The copper layer 12 formed a copper thin film layer by a sputtering method, and then formed a copper plating layer by a wet plating method using the copper thin film layer as a power feeding layer. Specifically, a copper thin film layer having a thickness of 100 nm was first formed on one surface of the transparent substrate 11 by a direct current sputtering method using a Cu target (manufactured by Sumitomo Metal Mining Co., Ltd.). Thereafter, a copper plating layer was laminated by 0.5 μm by electroplating to form a copper layer 12.

  Next, a blackening layer 13 was formed on the entire surface of the copper layer 12 by a sputtering method using a sintering target in the same manner as in Experimental Example 3.

  As described in Experimental Example 3, the blackening layer was formed using a sputtering apparatus (Model: SIH-450 manufactured by ULVAC, Inc.).

  Specific conditions for sputtering when forming the blackening layer will be described.

First, the transparent base material on which the copper layer was formed was set on a substrate holder, and the inside of the chamber was evacuated. In addition, the ultimate vacuum in the chamber before sputtering was 1.5 × 10 ⁻⁴ Pa.

  Next, argon gas and a mixed gas (mixed gas of oxygen and nitrogen) were supplied into the chamber so as to satisfy the gas ratio conditions in Table 11 for each experimental example. The substrate holder was rotated at a speed of 30 rpm.

  Then, DC power was applied to the target to produce a blackened layer.

  Note that the numerical sequence after the experimental number 4 of the experimental number is the same as the numerical sequence after the experimental example 3 among the experimental number numbers in the experimental example 3 shown in Table 9 and Table 10. Uses the same target as in the case of the corresponding experiment number in Experimental Example 3 and forms a blackened layer under the same gas ratio conditions. That is, the blackened layer is formed under the same conditions except for the film thickness.

  Here, the numerical arrangement after Experimental Example 4 means, for example, “3-1” in Experimental Example 4-3-1, and the numerical arrangement after Experimental Example 3- Means, for example, “3-1” in Experimental Example 3-3-1. For this reason, the numerical sequence after Experimental Example 4- and the numerical sequence after Experimental Example 3- are the same, and Experimental Example 4-3-1 and Experimental Example 3-3-1 use the same target. The blackening layer is formed under the same gas ratio condition.

  About each experimental example, the blackening layer was formed so that it might become the film thickness of the blackening layer shown in Table 11, and the electroconductive board | substrate was produced.

  Reflectance measurement was performed on the conductive substrate obtained by the above steps. The evaluation results are shown in Table 11 and FIG.

  Since the reflectance measurement was performed in the same manner as in Experimental Example 2, a specific description is omitted here.

As described above, the measurement is performed by irradiating light having a wavelength changed every 1 nm in a wavelength range of 350 nm or more and 780 nm or more, and measuring the reflectance for each wavelength. And what averaged the measurement result measured in each wavelength in the wavelength range of 350 nm or more and 780 nm or more is shown in Table 11 as a visible light average reflectance. Table 11 also shows the reflectance and lightness L ^* of light having a wavelength of 550 nm.

  Further, FIG. 6 shows the wavelength dependence of the reflectance when measured in the above wavelength range. FIG. 6 shows the measurement results for the conductive substrates of Experimental Example 4-3-1 to Experimental Example 4-3-3.

表１１に示した結果によると、実験例４−３−３において、波長５５０ｎｍにおける反射率が３０％を若干超える場合が観察されたものの、他の実験例はいずれも波長５５０ｎｍにおける反射率が２０％未満となっており、特に低くなることが確認できた。なお、図６によれば実験例４−３−３については、反射率の波長依存性が、実験例４−３−１、実験例４−３−２とは異なる挙動を示すことが確認できた。

According to the results shown in Table 11, although a case where the reflectance at a wavelength of 550 nm slightly exceeds 30% was observed in Experimental Example 4-3-3, all of the other experimental examples had a reflectance of 20 at a wavelength of 550 nm. It was confirmed that it was particularly low. In addition, according to FIG. 6, it can be confirmed that the wavelength dependency of the reflectivity in Experimental Example 4-3-3 exhibits a behavior different from that of Experimental Example 4-3-1 and Experimental Example 4-3-2. It was.

  In Experimental Example 4-3-1 to Experimental Example 4-4-3, the blackening layer was formed under the same conditions as in Experimental Example 3-3-1 to Experimental Example 3-4-3, respectively, except for the film thickness as described above. Is forming. For this reason, the blackening layer contained in the conductive substrate produced in Experimental Example 4-3-1 to Experimental Example 4-4-3 is evaluated in Experimental Example 3-3-1 to Experimental Example 3-4-3, respectively. It can be said that it has the same characteristics as the blackened layer subjected to. That is, the composition of the blackening layer formed on the conductive substrate manufactured in Experimental Example 4-3-1 to Experimental Example 4-4-3 and the sheet resistance are the same as in Experimental Example 3-3 evaluated in Experimental Example 3. -1 to Experimental Example 3-4-3.

  Further, as described in Experimental Example 3, the blackened layer evaluated in Experimental Example 3-3-1 to Experimental Example 3-4-3 exhibits the same solubility as the copper layer in the etching solution in the dissolution test. I was able to confirm. From this, the conductive substrates produced in Experimental Example 4-3-1 to Experimental Example 4-4-3 were each provided with a copper layer that could be etched simultaneously and a blackening layer. It can be said that it is a conductive substrate.

10A, 10B, 20A, 20B, 30 Conductive substrate 11, 11A, 11B Transparent base material 12, 12A, 12B Copper layer 13, 13A, 13B, 131, 132, 131A, 131B, 132A, 132B, 32A, 32B Blackening Layer 31A, 31B wiring

Claims (6)

A transparent substrate;
A copper layer formed on at least one surface of the transparent substrate;
The molybdenum content, which is formed on at least one surface side of the transparent substrate and is composed of oxygen, nitrogen, copper, nickel, and molybdenum, and the content of copper, nickel, and molybdenum is 100 atomic% And a blackened layer having 4 atomic% or more and 70 atomic% or less. The copper layer has a thickness of 100 nm or more,
The conductive substrate according to claim 1, wherein the blackened layer has a thickness of 20 nm or more.   The conductive substrate according to claim 1 or 2, wherein the reflectance of light having a wavelength of 550 nm is 30% or less.   The electroconductive board | substrate as described in any one of Claims 1 thru | or 3 provided with the mesh-shaped wiring. A transparent substrate preparation step of preparing a transparent substrate;
A copper layer forming step of forming a copper layer on at least one surface side of the transparent substrate;
When at least one surface side of the transparent substrate is composed of oxygen, nitrogen, copper, nickel and molybdenum, and the content of copper, nickel and molybdenum is 100 atomic%, the molybdenum content is 4 And a blackened layer forming step of forming a blackened layer that is at least 70 atom% and at least 70 atom%. The blackening layer forming step includes
Using a copper-nickel-molybdenum mixed sintered target,
6. The conductivity according to claim 5, wherein the blackened layer is formed by a sputtering method while supplying oxygen in a ratio of 5% by volume to 35% by volume and nitrogen in a ratio of 30% by volume to 70% by volume in the chamber. A method for manufacturing a substrate.

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