JP2016186928A - Manufacturing method of electric apparatus and electric apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of an electric apparatus capable of eliminating unevenness in an etching amount of a copper wiring and a blackened layer while maintaining good etching controlling property and further capable of suppressing a reflection factor over the whole wavelength of a visible ray, and provide the electric apparatus.SOLUTION: The manufacturing method of an electric apparatus comprises the processes of: forming a laminate membrane by laminating a Cu layer 2 and a CuNO-based blackened layer 3 in order on at least one main surface of a substrate 1; forming a resist layer 10 in a predetermined area on the laminate membrane; removing an area of the laminate membrane which is not covered by the resist layer by contacting the laminate membrane with an etching liquid; and forming a dielectric layer 4 on the substrate 1 and the patterned laminate membrane. A extinction coefficient of the CuNO-based blackened layer 3 at a wavelength of 400 nm to 700 nm is 1.0 to 1.8.SELECTED DRAWING: Figure 9

Description

  The present invention relates to a method for manufacturing an electric device and an electric device, and for example, relates to an electric device used as a wiring member for a touch panel or an electromagnetic shielding material.

  In recent years, with the advancement of functions and increased use of display devices, the need for improved development of touch panels and electromagnetic shielding materials attached to the surface of display devices has increased. In particular, since small devices such as smartphones and tablet terminals have a short distance between the user and the display device, demands for improving the visibility of the display device are increasing. For example, in the field of touch panels attached to the surface of a display device, it is superior in cost balance in place of conductive transparent materials (ITO, IZO, etc.) that have been mainly used as wiring materials, and compared to ITO, IZO, etc. Thus, studies have been made to use copper, aluminum, silver, gold, or the like, which has a resistance value 1 to 2 digits lower, as the wiring. For example, when copper wiring is used, when the touch panel is visually recognized from the outside, the presence of the copper wiring becomes conspicuous due to the reflection of the surface of the copper wiring. In order to prevent this, the surface of the copper wiring is blackened. The Also in the field of electromagnetic shielding materials, the surface of the copper wiring pattern is blackened for the same purpose.

  There are various manufacturing methods including blackening treatment in the manufacturing process of the touch panel and the electromagnetic wave shielding material. For example, the following methods are used.

  For example, Patent Document 1 includes a step of preparing a laminate having a conductive pattern layer made of a conductive composition containing silver particles and a binder resin on one side of a transparent substrate, and a hydrochloric acid solution in which tellurium is dissolved. The metal blackening solution having a tellurium concentration (oxide equivalent concentration) of 0.01 to 0.45% by weight and a hydrochloric acid concentration of 0.05 to 8% by weight in the hydrochloric acid solution. A method for producing a transparent conductive material including a step of forming a blackened layer by contacting a body is described.

  In Patent Document 2, pretreatment such as degreasing or acid treatment of the conductive base material is performed in the pretreatment tank, and then a metal is deposited on the conductive base material in the plating tank. A method is described in which a blackening treatment tank, a water washing tank, a rust prevention treatment tank, and a water washing tank are sequentially passed to blacken the surface of the metal deposited on the conductive substrate.

  Further, Patent Document 3 discloses a touch panel manufacturing method in which a mesh-like conductive thin wire of an upper sensor electrode having a metal or alloy layer and a blackened layer formed on the metal or alloy layer is formed by the following steps. A method of forming a metal layer or alloy layer on a transparent substrate, forming an electrode pattern on the metal layer or alloy layer, forming a blackening layer on the metal layer or alloy layer, other than an electrode The method includes a step of removing the blackening layer of the portion.

JP 2011-82211 A JP 2013-239722 A JP 2012-94115 A

  In the technology using a laminated structure of copper wiring (Cu layer) and blackened layer, when patterning materials having different chemical properties such as copper wiring and blackened layer by etching, etching of the copper wiring and blackened layer is performed. Due to the difference in speed, there is a problem that the etching amount is uneven. For example, (A) If the etching speed of the copper wiring is faster than the etching speed of the blackened layer, the Cu layer is likely to be removed over a wide area, so that the copper wiring becomes thin and as a result, the electrical resistance increases. End up. On the other hand, if the etching speed of (B) the blackened layer is faster than the etching speed of the copper wiring, the blackened layer is likely to be removed over a wide area. It is exposed without being covered. Therefore, the surface reflection suppression of the copper wiring, which is the original purpose of the blackened layer, is insufficient. It is conceivable to use an etching solution for patterning the copper wiring and an etching solution for patterning the blackened layer separately. In this case, however, the etching process increases and the process becomes complicated. there were.

  Normally, the blackened layer is less likely to be etched than the copper wiring, so that (A), that is, the copper wiring is thinned and the electrical resistance is increased. Although it is conceivable to devise an etching solution, for example, if an etching solution with a strong erosion power is used, the etching control becomes low. The line width of the street cannot be maintained.

  Moreover, although the electrode by which the blackening process like patent document 1-3 was made | formed has the effect of reducing the reflectance with respect to the wavelength of a part of visible light, it has a reflectance over the whole wavelength range of visible light. There is room for improvement in the method of low reflection treatment for obtaining an electrode with better visibility, not suppression.

  In view of such circumstances, the present invention eliminates an uneven etching amount between the copper wiring and the blackened layer while maintaining good etching controllability, and further suppresses the reflectance over the entire visible light wavelength range. An object of the present invention is to provide a manufacturing method and an electric device.

  The inventors conducted a test to remove a part of the various films formed by stacking a Cu layer, which is a material for copper wiring, and a blackened layer by wet etching. However, it has been found that a CuNO-based composition (CuNO, CuO, CuN) may be used as a material for the blackening layer whose etching speed is close to that of Cu.

  Further, the present inventors have described examples of the extinction coefficient and the reflectance of each blackening layer described later when various blackening layers are formed by sputtering while changing the conditions of the introduction amounts of oxygen gas and nitrogen gas. We investigated as follows. As a result, it was found that the reflectance can be suppressed by using a blackened layer having an extinction coefficient of 1.0 or more and 1.8 or less obtained by controlling the composition ratio of the introduced gas. In addition to such a blackened layer, it has been found that the reflectance can be further suppressed by laminating a dielectric layer having a refractive index different from that of the blackened layer.

  The manufacturing method of an electrical device that can solve the above problems includes a step of forming a laminated film in which a Cu layer and a CuNO-based blackened layer are sequentially laminated on at least one main surface of a base material, Forming a resist layer in a predetermined region, removing the region of the laminated film that is not covered with the resist layer by contacting the laminated film with an etching solution, and forming a dielectric on the substrate and the patterned laminated film And a step of forming a body layer, wherein the extinction coefficient of the CuNO blackening layer at a wavelength of 400 nm to 700 nm is 1.0 or more and 1.8 or less. Since the manufacturing method of the electric device according to the present invention uses a CuNO blackening layer having an etching speed close to that of the Cu layer as the blackening layer, a part of the laminated film of the Cu layer and the CuNO blackening layer is etched. Even if removed, the widths of the remaining Cu layer and CuNO blackening layer can be made close to each other. Further, in the method for manufacturing an electrical device of the present invention, a CuNO-based blackening layer having an extinction coefficient of 1.0 to 1.8 in the visible light wavelength range of 400 nm to 700 nm is used. The reflectance can be suppressed as a whole. Furthermore, since the dielectric layer is laminated on the base material and the laminated film for preventing reflection of visible light, the reflectance can be reduced to 5% or less.

  In the method for manufacturing the electrical device, the CuNO-based blackened layer is preferably a CuNO blackened layer. This is because the etching speed between the Cu layer and the blackened layer can be made closer.

In the method for manufacturing the electric device, the dielectric layer is preferably a SiO ₂ layer. This is because SiO ₂ is easy to manufacture and has a stable structure, so that it is easy to handle.

  The step of forming the CuNO-based blackening layer is preferably performed by sputtering Cu in an atmosphere in which at least nitrogen gas and oxygen gas are present. This makes it possible to easily form a CuNO-based blackening layer that is a Cu layer incorporating nitrogen and oxygen atoms.

  In the step of removing a partial region of the laminated film of the Cu layer and the CuNO-based blackening layer, it is also preferable that the laminated film has a mesh pattern. By forming the Cu layer and the CuNO blackening layer in a mesh pattern, the light transmittance of the electric device can be increased, so that the reflectance can be suppressed.

  The electric device of the present invention that has solved the above problems is a laminated film in which a Cu layer and a CuNO-based blackening layer are sequentially laminated and patterned on at least one main surface of the substrate. And a dielectric layer formed on the substrate and the patterned laminated film, and the extinction coefficient of the CuNO blackening layer at a wavelength of 400 nm to 700 nm is 1.0 or more and 1.8 or less It has a gist at a certain point. Since the electrical device of the present invention uses a CuNO-based blackened layer whose etching speed is close to that of the Cu layer as the blackened layer, a part of the laminated film of the Cu layer and the CuNO-based blackened layer is removed by etching. Also, the widths of the remaining Cu layer and CuNO blackening layer can be made close to each other. In the electrical device of the present invention, a CuNO-based blackening layer having an extinction coefficient of 1.0 to 1.8 in the visible light wavelength range of 400 nm to 700 nm is used. The reflectance can be suppressed. Furthermore, since the dielectric layer is laminated on the base material and the laminated film for preventing reflection of visible light, the reflectance can be reduced to 5% or less.

  In the electric device, the CuNO blackening layer is preferably a CuNO blackening layer. This is because the etching speed between the Cu layer and the blackened layer can be made closer.

In the above electric device, the dielectric layer is preferably a SiO ₂ layer. This is because SiO ₂ is easy to manufacture and has a stable structure, so that it is easy to handle.

  In the above electric device, it is also preferable that the total film thickness of the CuNO blackening layer and the dielectric layer is 100 nm or less. If the total film thickness of the CuNO blackening layer and the dielectric layer exceeds 100 nm, an ACF (anisotropic conductive film) used for electrical connection and mechanical bonding between the base material such as FPC (flexible printed circuit board) and the Cu layer This is because it becomes difficult for the inner conductive particles to penetrate the CuNO-based blackening layer and the dielectric layer, making it difficult to electrically connect the base material and the Cu layer.

  Since the manufacturing method and the manufacturing apparatus of the electrical device of the present invention use a CuNO blackening layer whose etching speed is close to that of the Cu layer as the blackening layer, etching is performed on a part of the Cu layer and the CuNO blackening layer. Even if removed, the widths of the remaining Cu layer and CuNO blackening layer can be made close to each other. Moreover, since the electrical device of the present invention uses a CuNO-based blackening layer having an extinction coefficient of 1.0 to 1.8 in the visible light wavelength range of 400 nm to 700 nm, The reflectance can be suppressed. Furthermore, since the dielectric layer is also laminated on the base material and the CuNO blackening layer for preventing reflection of visible light, the reflectance as a laminated film can be reduced to 5% or less.

FIG. 1 is a plan view of a capacitive touch sensor according to an embodiment of the present invention. FIG. 2 is a process cross-sectional view of the method of manufacturing the electrical device according to the embodiment of the present invention. FIG. 3 is a process cross-sectional view of the method of manufacturing the electrical device according to the embodiment of the present invention. FIG. 4 is a cross-sectional view (partial side view) of a sputtering apparatus applicable to the method for manufacturing an electrical apparatus according to an embodiment of the present invention. FIG. 5 is a process cross-sectional view of the method for manufacturing the electrical device according to the embodiment of the present invention. FIG. 6 is a process cross-sectional view of the method of manufacturing the electrical device according to the embodiment of the present invention. FIG. 7 is a process cross-sectional view of the method for manufacturing the electrical device according to the embodiment of the present invention. FIG. 8 is a process cross-sectional view of the method of manufacturing the electrical device according to the embodiment of the present invention. FIG. 9 is a process cross-sectional view of the method of manufacturing the electrical device according to the embodiment of the present invention. FIG. 10 is a cross-sectional view of another electric device according to the embodiment of the present invention. FIG. 11 is a cross-sectional view of another electric device according to the embodiment of the present invention. FIG. 12 is a cross-sectional view of another electric device according to the embodiment of the present invention. FIG. 13 is a cross-sectional view of another electric device according to the embodiment of the present invention. FIG. 14 is a conceptual diagram showing a method for measuring single-sided reflectance and transmittance of a sample according to the present invention. FIG. 15 is a conceptual diagram showing a method for measuring single-sided reflectance and transmittance of a sample according to the present invention. FIG. 16 is a graph showing an extinction coefficient at a wavelength of 400 nm to 700 nm in Example 1 according to the present invention. FIG. 17 is a graph showing the extinction coefficient of Comparative Example 1 according to the present invention at wavelengths of 400 nm to 700 nm. FIG. 18 is a graph showing the extinction coefficient at a wavelength of 400 nm to 700 nm in Comparative Example 2 according to the present invention. FIG. 19 is a graph showing the reflectance at a wavelength of 400 nm to 700 nm in Example 1 according to the present invention. FIG. 20 is a graph showing the reflectance at a wavelength of 400 nm to 700 nm in Comparative Example 1 according to the present invention. FIG. 21 is a graph showing the reflectance at a wavelength of 400 nm to 700 nm in Comparative Example 2 according to the present invention. FIG. 22 is a graph showing the reflectance at a wavelength of 400 nm to 700 nm in Comparative Example 3 according to the present invention. FIG. 23 is a graph showing the reflectance at a wavelength of 400 nm to 700 nm in Comparative Example 4 according to the present invention. FIG. 24 is a graph showing the reflectance at a wavelength of 400 nm to 700 nm in Comparative Example 5 according to the present invention. FIG. 25 is a graph showing the reflectance at a wavelength of 400 nm to 700 nm in Comparative Example 6 according to the present invention. FIG. 26 is a graph showing the reflectance at a wavelength of 400 nm to 700 nm in Comparative Example 7 according to the present invention. FIG. 27 is a graph showing the reflectance at a wavelength of 400 nm to 700 nm in Comparative Example 8 according to the present invention.

  Hereinafter, the present invention will be described more specifically on the basis of the embodiments. However, the present invention is not limited by the following embodiments, but may be implemented with modifications within a range that can meet the purpose described above and below. Of course, any of these is also included in the technical scope of the present invention. In addition, the dimensional ratios of various members in the drawings are given priority to contribute to understanding the characteristics of the present invention, and may be different from the actual dimensional ratios.

  The present invention is not limited to applications such as a touch panel and an electromagnetic shielding material, but can be applied to an electric device having a CuNO-based blackening layer. Here, the present invention will be described by taking a capacitive touch sensor as an example.

  FIG. 1 is a plan view of a capacitive touch sensor 100 which is an example of the electric apparatus of the present invention. As shown in FIG. 1, a capacitive touch sensor 100 according to the present embodiment is formed on a surface of a resin sheet 111 made of, for example, polycarbonate and a resin sheet 111, and a conductive material for detecting a vertical key input. Part 112, formed on the back surface of resin sheet 111, conductive part 113 for detecting lateral key input, connector part 115, and lead electrode 114 connecting each conductive part 112, 113 and connector part 115. And mainly. The connector unit 115 is connected to the control unit 116, and the operation of the capacitive touch sensor 100 is controlled by the control unit 116. Each of the conductive portions 112 and 113 is formed in a mesh pattern as shown in a partially enlarged view in FIG. 1 in order to allow light transmission. In addition to the mesh pattern, a stripe pattern, a wave pattern having a wavy stripe pattern, or a punching pattern having a plurality of holes may be used.

  The conductive portions 112 and 113 formed on the front and back surfaces of the resin sheet 111 are formed of a Cu layer. In order to suppress light reflection by the Cu layer, the conductive portions 112 and 113 include a CuNO-based blackening layer and A dielectric layer is formed. The aspect in which the conductive portions 112 and 113 are formed on the front and back of the resin sheet 111 is an example of a capacitive touch sensor to which the present invention can be applied, and hereinafter, at least one of the resin sheets 111 (base material). The present invention including a step of forming a laminated film of a Cu layer, a CuNO-based blackening layer, and a dielectric layer on the main surface will be described.

  The method for manufacturing an electric device according to an embodiment of the present invention includes (1) forming a laminated film in which a Cu layer and a CuNO-based blackening layer are sequentially laminated on at least one main surface of a substrate; (2) a step of forming a resist layer in a predetermined region on the CuNO-based blackened layer, and (3) the stacked layer of the Cu layer and the CuNO-based blackened layer is brought into contact with an etching solution to bring the stacked layer into the resist layer. A step of removing an uncovered region; and (4) a step of forming a dielectric layer on the substrate and the patterned laminated film, and extinction at a wavelength of 400 nm to 700 nm of the CuNO-based blackening layer The coefficient is 1.0 or more and 1.8 or less.

  Moreover, the electric device according to the embodiment of the present invention includes a base material, and a laminated film in which a Cu layer and a CuNO-based blackening layer are sequentially laminated and patterned on at least one main surface of the base material. And a dielectric layer formed on the substrate and the patterned laminated film, and the extinction coefficient of the CuNO blackening layer at a wavelength of 400 nm to 700 nm is 1.0 or more and 1.8 or less.

  Since the manufacturing method of the electric device of the present invention and the electric device use a CuNO-based blackening layer whose etching speed is close to that of the Cu layer as the blackening layer, a part of the Cu layer and the CuNO-based blackening layer is etched. Even if removed, the widths of the remaining Cu layer and CuNO blackening layer can be made close to each other. In addition, since a CuNO-based blackening layer having an extinction coefficient of 1.0 to 1.8 in the visible light wavelength range of 400 nm to 700 nm is used, the reflectance in the entire wavelength range can be suppressed. . Furthermore, since the dielectric layer is laminated on the base material and the CuNO blackening layer for preventing reflection of visible light, the reflectance can be reduced to 5% or less.

The CuNO-based blackening layer in the present invention is a compound containing Cu, N (nitrogen) and / or O (oxygen), and the balance of inevitable impurities. Typically, CuNO, Cu ₃ N, CuO , Cu ₂ O compositions. The blackening layer also has an effect of attenuating the intensity of light propagating inside, but there is an element that suppresses reflected light mainly by the effect of interference of reflected visible light.

  The dielectric layer increases the transmittance of visible light and decreases the reflectance. The minimum reflection wavelength of the dielectric layer is determined by the refractive index and film thickness of the material of the dielectric layer. In the present invention, since the CuNO blackening layer and the dielectric layer having a refractive index different from that of the blackening layer are combined, the reflectance is kept low at visible light wavelengths of 400 nm to 700 nm.

  The extinction coefficient at a wavelength of 400 nm to 700 nm of the CuNO blackening layer according to the present invention is 1.0 or more and 1.8 or less. The extinction coefficient of the CuNO blackening layer is set to 1.0 or more and 1 by setting the nitrogen existing ratio in the CuNO blackening layer to 0.8 at% to 4 at% and the oxygen existing ratio to 4 at% to 10 at%. .8 or less.

  Hereinafter, a preferable example of the method for manufacturing the electrical wiring member according to the present embodiment will be described in detail with reference to the drawings. 2 to 3 are process cross-sectional views illustrating a part of the method for manufacturing the electrical wiring member according to the present embodiment.

(1) Step of forming a laminated film in which a Cu layer and a CuNO blackening layer are sequentially laminated As shown in FIG. 2, a Cu layer 2 is formed on at least one main surface of a substrate 1. Next, a CuNO-based blackening layer 3 is formed on the Cu layer 2 as shown in FIG. By these steps, a laminated film of the Cu layer 2 and the CuNO blackening layer 3 is formed on at least one main surface of the substrate 1. Further, the CuNO-based blackening layer 3 may be only one layer as shown in FIG. 3, or two layers may be included. However, the total film thickness of the CuNO-based blackening layer formed on at least one main surface of the substrate is preferably 5 nm to 150 nm. More preferably, it is 12 nm-115 nm, More preferably, it is 18 nm-80 nm.

  The blackening layer also has an effect of attenuating the intensity of light propagating inside, but there is an element that suppresses reflected light mainly by the effect of interference of reflected visible light. When the total film thickness of the CuNO blackening layer and the dielectric layer exceeds 100 nm, the conductive particles in the ACF used for electrical connection and mechanical adhesion between the base material such as FPC and the Cu layer are in contact with the CuNO blackening layer and the dielectric. Since it becomes difficult to penetrate the body layer and it is difficult to electrically connect the base material and the Cu layer, the film thickness of the CuNO-based blackening layer 3 is preferably within the above range.

  It is also preferable that the CuNO-based blackened layer is a CuNO blackened layer. This is because the etching speed between the Cu layer and the blackened layer can be made closer.

  The thickness of the Cu layer 2 is set to, for example, 20 nm or more, preferably 40 nm or more, and more preferably 60 nm or more, in order to ensure necessary electric conductivity. However, if the Cu layer 2 is too thick, it takes too much time for etching, so that it is, for example, 2 μm or less, preferably 1 μm or less, more preferably 400 nm or less.

  The material used for the substrate 1 is not particularly limited as long as it is a non-conductive material. For example, polyethylene terephthalate resin (PET), aliphatic cyclic polyolefin resin (COP), glass, polycarbonate resin (PC), Acrylic resin (PMMA) or the like can be used. When the electric wiring member is used for a display device, it is desirable that the base material 1 is substantially transparent. Although there is no restriction | limiting in particular in the thickness of the base material 1, For example, they are 15 micrometers-200 micrometers, Preferably they are 20 micrometers-150 micrometers, More preferably, you may be 25 micrometers-125 micrometers.

  The method for forming the Cu layer 2 or the CuNO-based blackening layer 3 is not particularly limited, but can be formed by sputtering, vapor deposition, CVD, or the like, and can also be formed by modifying the surface of the Cu layer. Is possible. In this embodiment, a stacked film formation method using a sputtering method will be described as an example.

FIG. 4 is a cross-sectional view of a sputtering apparatus 50 that is an apparatus for manufacturing an electrical wiring member according to the present embodiment. The sputtering apparatus 50 is divided by a sealed casing 51, a substrate unwinding reel 52 formed in the sealed casing 51, a substrate take-up reel 53, and a partition wall 54 formed in the sealed casing 51. A first compartment 55 and a second compartment 56 adjacent to the first compartment 55. A Cu target material 57 is disposed in the first compartment 55 and the second compartment 56. The first compartment 55 is formed with an argon gas inlet 58 for collision with the Cu target material 57. An oxygen gas and / or nitrogen gas inlet 59 is formed in the second compartment 56, but argon gas can also be supplied. In addition to the argon gas, hydrogen gas (H ₂ ) can be introduced at the introduction port 59 in order to promote the incorporation of nitrogen into the blackened layer.
The sealed casing 51 is provided with a low vacuum suction port 65 and a high vacuum suction port 66. The low vacuum suction port 65 is connected to, for example, an oil rotary vacuum pump (not shown), and can quickly depressurize the inside of the sealed casing 51 to a certain degree of vacuum. The high vacuum suction port 66 is connected to, for example, a turbo molecular pump (not shown), and can reduce the pressure inside the sealed casing 51 to a high vacuum level that allows sputtering.

  The base material unwinding reel 52 holds the base material 1 described above in a roll shape. The base material 1 starts from the base material take-up reel 52, and is finally wound around the base material take-up reel 53 via the pinch roll 60, the inner drum 61, and the pinch roll 62.

  The Cu target material 57 arranged in the first compartment 55 to the second compartment 56 is connected to the controller 64 by a conducting wire 63 in order to apply a predetermined potential. As a sputtering method, DC sputtering in which a DC voltage is applied between two electrodes, RF sputtering in which a high frequency is applied, magnetron sputtering, or ion beam sputtering can also be used.

  A Cu layer is formed on the substrate 1 unwound from the substrate unwinding reel 52 and entering the first compartment 55 by sputtering of the Cu target material 57 (FIG. 2). Since only the introduction port 58 for argon gas, which is an inert gas, is formed in the first compartment 55, oxygen and / or nitrogen is basically not taken into the Cu layer 2 (inevitable mixing). Except what you do).

  Next, when the base material 1 enters the second compartment 56, a Cu layer is formed by sputtering of the Cu target material 57. At this time, since oxygen gas and / or nitrogen gas is supplied to the second compartment 56 from the inlet 59, the film formed on the Cu layer 2 is oxygen (O) and / or nitrogen. (N) A CuNO-based blackening layer 3 that is a Cu layer incorporating atoms (FIG. 3). That is, the step of forming the CuNO-based blackening layer is preferably performed by sputtering Cu in an atmosphere in which at least nitrogen gas and oxygen gas are present. The existing ratio of nitrogen gas / oxygen gas can be, for example, 21% / 9% and 15% / 12%.

  In the same procedure, the Cu layer 2 and the CuNO-based blackening layer 3 can be formed also on the back side of the substrate 1. For example, the substrate roll wound up on the substrate take-up reel 53 after completing the process of FIG. 3 is transferred to the substrate unwinding reel 52 so that the back surface side of the substrate 1 faces the Cu target material 57 side. set. The base material 1 is pulled out from the base material take-up reel 52, and finally set on the base material take-up reel 53 via the pinch roll 61, the inner drum 62, and the pinch roll 63. By operating the sputtering apparatus 50 in this state, as shown in FIG. 5, the Cu layer 2 and the CuNO blackening layer 3 can be formed also on the back surface side of the base material 1.

  From the viewpoint of effective use of one manufacturing apparatus, a method of replacing the base roll from the base take-up reel 53 to the base take-up reel 52 as described above can be preferably implemented. From the viewpoint of speeding up, compartments (for example, a third compartment to a fourth compartment (not shown) following the second compartment) that can also form a film on the back side of the substrate 1 in the same sealed casing 51. )), Or another sputtering apparatus (not shown) that can form a film on the back side of the substrate 1 separately from the sputtering apparatus 50.

  In the above description, the oxygen gas and / or nitrogen gas inlet 59 is provided in the second compartment 56 in order to stack the Cu layer 2 / CuNO-based blackening layer 3 shown in FIG. It is.

(2) Step of Forming Resist Layer in Predetermined Region on CuNO-Based Blackening Layer FIGS. 6 to 9 are process cross-sectional views illustrating a part of the method for manufacturing the electrical device according to the present embodiment. First, as shown in FIG. 6, the resist layer 10 is uniformly formed in a predetermined region on the CuNO blackening layer. The material used for the resist layer 10 is not particularly limited, and a semi-solid (paste-like) or solid (film-like) material can be used.

  Next, the resist layer 10 is patterned using a lithography method or the like as shown in FIG. The step of partially removing the resist layer typically involves irradiating a part of the resist layer with light and removing the irradiated part with a developer (positive photoresist), or using light. This is realized by removing a portion that is not irradiated with a developing solution (negative photoresist).

(3) Step of removing partial regions of Cu layer and CuNO-based blackening layer As shown in FIG. 8, etching solution is used to remove the exposed Cu layer 2 and CuNO-based blackening layer 3 without being covered with the resist layer 10. It is possible to remove a part of the Cu layer 2 and a part of the CuNO-based blackening layer 3 by contacting them. The etching solution to be used is not particularly limited as long as both the Cu layer and the CuNO blackening layer can be etched, but in order to maintain the etching controllability to some extent, it is necessary to control the etching rate. It is desirable to adjust the temperature, concentration, pH and the like. After the partial regions of the Cu layer 2 and the CuNO-based blackening layer 3 are removed, the remaining resist layer 10 is removed using a cleaning liquid.

  In the step of removing a partial region of the Cu layer 2 and the CuNO-based blackening layer 3, the Cu layer 2 and the CuNO-based blackening layer 3 include a mesh pattern, a stripe pattern, a wave pattern in which the stripes are wavy, and the like. It is also preferable to form with a punching pattern having a plurality of holes. Thereby, the light transmittance of an electric apparatus can be raised.

(4) Step of Forming Dielectric Layer on Base Material and Patterned Laminated Film As shown in FIG. 9, the dielectric layer 4 is formed on the exposed base material 1 and the patterned laminated film. That is, in the electric device, the Cu layer 2, the CuNO blackening layer 3, and the dielectric layer 4 are laminated in this order from the side facing the base material. In order to suppress reflection of light by the Cu layer 2, a CuNO-based blackening layer 3 is laminated on the Cu layer 2. In addition, the dielectric layer 4 effective for preventing reflection is further laminated on the base material 1 and the patterned laminated film, thereby reflecting the Cu layer 2, the CuNO-based blackening layer 3, and the dielectric layer 4 as a whole. The rate can be reduced.

The material of the dielectric layer 4 is not particularly limited, and for example, SiO, SiO ₂ , TiO ₂ , Al ₂ O ₃ , Ta ₂ O ₅ , Nb ₂ O ₅ , ZrO ₂ , HfO ₂ , La ₂ O ₃ , Cr ₂ Oxides such as O ₃ , CeO ₂ , Y ₂ O ₃ , ZnO, and ITO, fluorides such as CaF ₂ and MgF ₂ , and nitrides such as Si ₃ N ₄ can be used. In particular, the dielectric layer 4 is preferably a SiO ₂ layer. This is because SiO ₂ is easy to manufacture and has a stable structure, so that it is easy to handle.

  The thickness of the dielectric layer 4 is preferably 10 nm to 200 nm. More preferably, it is 18 nm-100 nm, More preferably, it is 36 nm-70 nm. It is also preferable that the total film thickness of the CuNO-based blackening layer 3 and the dielectric layer 4 is 100 nm or less. When the total film thickness of the CuNO blackening layer 3 and the dielectric layer 4 exceeds 100 nm, it is difficult to press-bond the CuNO blackening layer 3 and the dielectric layer 4, and it is difficult to conduct with the Cu layer 2. is there.

The method of forming the dielectric layer 4 on the base material 1 and the patterned laminated film is the same as the method of forming the Cu layer 2 or the CuNO-based blackening layer 3 on the base material 1. It can be formed by a CVD method or the like. For example, if an Si target material is sputtered while introducing oxygen gas in a compartment of a sputtering apparatus in a vacuum state, a SiO ₂ layer as a dielectric layer 4 is formed on the base material 1 and the CuNO-based blackening layer 3. be able to.

  An electrical device different from the electrical device shown in FIG. 9 will be described with reference to FIGS. In the description of FIGS. 10 to 13, the description overlapping with the above description is omitted. 10 to 13 are sectional views of the electric device according to the embodiment of the present invention.

  In the electric device shown in FIG. 10, the Cu layer 2a and the CuNO blackening layer 3a are sequentially laminated on one main surface of the base material 1, the laminated film is patterned, and the base material 1 and the patterned laminated film are obtained. A dielectric layer 4a is formed thereon. Further, a Cu layer 2b and a CuNO-based blackening layer 3b are sequentially laminated on the other main surface of the substrate 1, and the laminated film is patterned. A dielectric layer is formed on the substrate 1 and the patterned laminated film. 4b is formed. In addition, the extinction coefficient in wavelength 400nm-700nm of CuNO type | system | group blackening layer 3a, 3b is 1.0 or more and 1.8 or less, respectively. In the electric device shown in FIG. 10, since the CuNO blackening layer 3a and the dielectric layer 4a are laminated on the Cu layer 2a formed on one main surface of the substrate 1, the dielectric shown in FIG. The reflectance when visible light is incident from the layer 4a side can be 5% or less. Further, since the CuNO blackening layer 3b and the dielectric layer 4b are also laminated on the Cu layer 2b formed on the other main surface of the substrate 1, it is visible from the dielectric layer 4b side in FIG. Even when a light beam is incident, the reflectance can be reduced to 5% or less. That is, by configuring the electric device as shown in FIG. 10, the reflectance when visible light is incident can be reduced to 5% or less on both sides of the electric device.

The electrical device shown in FIG. 11 is an example in which a dielectric layer 5 and a CuNO-based blackening layer 3b are further laminated between the base material 1 and the Cu layer 2 of the electrical device shown in FIG. In this electrical device, a dielectric layer 5, a CuNO-based blackened layer 3b, a Cu layer 2, and a CuNO-based blackened layer 3a are sequentially stacked on one main surface of the substrate 1, and the dielectric layer 5, A dielectric layer 4 is formed on the laminated film of the patterned CuNO blackening layer 3b, Cu layer 2, and CuNO blackening layer 3a. As described above, in the electric device shown in FIG. 11, since the CuNO-based blackening layer 3a and the dielectric layer 4 are laminated on the upper side of the Cu layer 2, one main surface side of the substrate 1 (the dielectric shown in FIG. 11). The reflectance when visible light is incident from the body layer 4 side) can be lowered. Moreover, since the CuNO type | system | group blackening layer 3b and the dielectric material layer 5 are laminated | stacked also on the lower side of the Cu layer 2, the electrical apparatus is from the other main surface side (base material 1 side of FIG. 11) of the base material 1. Even if visible light is incident, the reflectance can be lowered. When the electric device is configured as described above, the material of the dielectric layer 4 is not particularly limited, but in order to reduce the reflectance when the visible light is incident from one main surface side of the base material 1 to 5% or less. It is preferable to use SiO ₂ or Al ₂ O ₃ having a low refractive index. On the other hand, the material of the dielectric layer 5 is made of TiO ₂ or Ta ₂ O ₅ having a high refractive index in order to reduce the reflectance when the visible light is incident from the other main surface side of the substrate 1. Nb ₂ O ₅ , ZrO ₂ , HfO ₂ , La ₂ O ₃ , Cr ₂ O ₃ , CeO ₂ , Y ₂ O ₃ , ZnO, ITO, SiO, Si ₃ N _4, etc. can be used. In order to reduce the reflectance when visible light is incident from the other main surface side of 1 to 5% or less, it is preferable to use a material having a higher refractive index, for example, TiO ₂ among others.

In the electric device shown in FIG. 12, the dielectric layer 5, the CuNO blackening layer 3b, and the Cu layer 2b are sequentially laminated on the other main surface of the substrate 1 of the electric device shown in FIG. In this example, the layer 3b and the Cu layer 2b are patterned. In the electric device shown in FIG. 12, a CuNO-based blackening layer 3a and a dielectric layer 4 are formed on the upper side of the Cu layer 2a on one main surface of the substrate 1 in the same manner as the electric device shown in FIG. Therefore, the reflectance on the upper side surface of the Cu layer 2a when visible light is incident from one main surface side (the dielectric layer 4 side in FIG. 12) of the substrate 1 can be lowered. In addition, since the dielectric layer 5 and the CuNO-based blackening layer 3b are formed on the other main surface of the base material 1, this electric device has one main surface side of the base material 1 (the dielectric body shown in FIG. 12). The reflectance on the upper surface of the Cu layer 2b when visible light is incident from the layer 4 side can also be lowered. Such an electric device is suitable for the case where Cu layers are arranged on both main surfaces of the base material and the reflectance of the Cu layer is desired to be lowered when visible light is incident from one main surface side of the base material 1. ing. The material of the dielectric layer 4 is not particularly limited, as is the case with the dielectric layer 4 of the electric device shown in FIG. 11, but it is preferable to use SiO ₂ or Al ₂ O ₃ having a low refractive index. On the other hand, the material of the dielectric layer 5 is TiO ₂ , Ta ₂ O ₅ , Nb ₂ O ₅ , ZrO ₂ , HfO having a high refractive index, like the dielectric layer 5 of the electric device shown in FIG. ₂ , La ₂ O ₃ , Cr ₂ O ₃ , CeO ₂ , Y ₂ O ₃ , ZnO, ITO, SiO, Si ₃ N _4, etc. can be used, among which a material having a higher refractive index, for example, TiO ₂ is preferably used.

The electric device shown in FIG. 13 is an example in which the structure formed on one main surface of the base material 1 of the electric device shown in FIG. In the electric device shown in FIG. 13, a dielectric layer 5a, a CuNO-based blackened layer 3b, a Cu layer 2a, and a CuNO-based blackened layer 3a are sequentially stacked on one main surface of the substrate 1 to form a dielectric layer. A dielectric layer 4a is formed on the laminated film of 5a, the patterned CuNO blackening layer 3b, the Cu layer 2a, and the CuNO blackening layer 3a. Further, on the other main surface of the substrate 1, a dielectric layer 5b, a CuNO blackening layer 3c, a Cu layer 2b, and a CuNO blackening layer 3d are sequentially laminated, and patterned with the dielectric layer 5b. A dielectric layer 4b is formed on the laminated film of the CuNO blackening layer 3c, the Cu layer 2b, and the CuNO blackening layer 3d. For this reason, when visible light is incident from one main surface side of the substrate 1 (dielectric layer 4a side in FIG. 13), the reflectance on the upper side surface of the Cu layer 2a and the upper side surface of the Cu layer 2b is lowered. be able to. Further, even when visible light is incident from the other main surface side of the substrate 1 (dielectric layer 4b side in FIG. 13), the reflectance on the lower side surface of the Cu layer 2a and the lower side surface of the Cu layer 2b is reduced. Can do. Such an electric device is suitable for the case where Cu layers are arranged on both main surfaces of the base material and the reflectance when the visible light is incident from both main surface sides of the base material is desired to be lowered. The material of the dielectric layers 4a and 4b is not particularly limited as in the case of the dielectric layer 4 of the electric device shown in FIG. 11, but it is preferable to use SiO ₂ or Al ₂ O ₃ having a low refractive index. On the other hand, the material of the dielectric layer 5 is TiO ₂ , Ta ₂ O ₅ , Nb ₂ O ₅ , ZrO ₂ , HfO having a high refractive index, like the dielectric layer 5 of the electric device shown in FIG. ₂ , La ₂ O ₃ , Cr ₂ O ₃ , CeO ₂ , Y ₂ O ₃ , ZnO, ITO, SiO, Si ₃ N _4, etc. can be used, among which a material having a higher refractive index, for example, TiO ₂ is preferably used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, and appropriate modifications are made within a range that can be adapted to the above-described purpose. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.

[Test method]
Various electric devices (samples) having a base material and a laminated film were prepared, (A) an extinction coefficient at a wavelength of 400 nm to 700 nm, (B) a reflectance at a wavelength of 400 nm to 700 nm, (C) a blackening layer and a Cu layer, A test for confirming the etching control property was conducted.

[Sample preparation]
After forming a 100 nm thick Cu layer on a PET substrate having a thickness of 50 μm and a width of 20 mm × 70 mm by sputtering, a blackened layer (CuNO blackened layer, CuO blackened layer, CuN blackened layer or NiCu blackened layer) Layer). Next, the sample is immersed in a beaker containing a liquid etchant at room temperature, and the blackened layer formed by sputtering is etched. A dielectric layer (SiO ₂ layer, or SiO ₂ layer and TiO ₂ layer) was formed on the etched Cu layer and blackening layer. Depending on the sample, the blackening layer and / or the dielectric layer were not stacked. Samples include: Sample 1: SiO ₂ / CuNO / Cu, Sample 2: CuNO / Cu, Sample 3: SiO ₂ / CuO / Cu, Sample 4: Cu, Sample 5: CuO / Cu, Sample 6: CuN / Cu, Sample 7: SiO ₂ / TiO ₂ / Cu, Sample 8: SiO ₂ / TiO ₂ / SiO ₂ / TiO ₂ / SiO ₂ / TiO ₂ / SiO ₂ / TiO ₂ / Cu _, Sample 9: 9 types of NiCu / Cu Using. The sputtering conditions for forming the blackened layer are as follows.
Input power: 9 kW (9.4 W / cm ² )

(A) Extinction coefficient measurement test In Table 1, "Extinction coefficient" is an extinction coefficient at a wavelength of 400 nm to 700 nm of the blackened layer, and was specified in detail as follows. The extinction coefficient is determined from the film thickness d (nm) obtained by observing the cross section of the CuNO blackening layer, the single-sided reflectance R ₀ (%), and the transmittance T (%) obtained by spectroscopic measurement. The extinction coefficient is calculated according to the following procedures (A-1) to (A-4). In this test, it was confirmed whether the extinction coefficient k was 1.0 or more at wavelengths of 400 nm to 700 nm.

(A-1) Preparation of measurement sample A sample for measuring the extinction coefficient k (hereinafter referred to as a sample obtained by forming a CuNO-based blackened layer having a thickness of 40 nm to 100 nm on a polyolefin copolymer film substrate having a thickness of 200 μm) Or simply referred to as “sample”).

(A-2) Measurement of the film thickness of the CuNO-based blackening layer Focused ion beam processing observation apparatus (Part No .: FB2200; manufactured by Hitachi High-Technologies Corporation) and super-resolution field emission scanning electron microscope (Part No .: SU8010; Hitachi High-Technologies Corporation) The film thickness d of the CuNO blackening layer is obtained by observing the cross section of the CuNO blackening layer using

(A-3) Measurement of single-sided reflectance and transmittance of sample Using a spectrophotometer (product number: U-4100; manufactured by Hitachi High-Technology Corporation), single-sided reflectance R ₀ (%) of a sample at a wavelength of 400 nm to 700 nm And the transmittance T (%). 14 and 15 are conceptual diagrams showing a method for measuring the single-sided reflectance R ₀ and transmittance T of a sample according to the present invention. As shown in FIG. 14, when incident light 20 (visible light) is incident from the CuNO blackening layer 2 side of the sample composed of the substrate 1 and the CuNO blackening layer 2, the surface of the CuNO blackening layer 2 , Reflected light 22 at the interface between the base material 1 and the CuNO-based blackening layer 2, and reflected light 23 at the back surface of the base material are generated. The outgoing light 24 is the outgoing light after the incident light has passed through the CuNO-based blackening layer 2, and the outgoing light 25 is the outgoing light after the incident light 20 has passed through the CuNO-based blackening layer 2 and the substrate 1. It is.

The single-sided reflectance R ₀ of the sample is the sum of the reflectance of the reflected light 21 and the reflectance of the reflected light 22. As shown in FIG. 15, in the measurement of the single-sided reflectance R ₀ , the back surface of the base material 1 is matted and sanitized, and the antireflection layer 26 is formed to remove the reflected light 23 on the back surface of the base material. can do. The transmittance T of the sample is the ratio of the intensity of the outgoing light 25 to the intensity of the incident light 20.

(A-4) Calculation of extinction coefficient The extinction coefficient k is calculated | required from the following Numerical formulas 1 and 2. FIG. T _i is an internal transmittance of CuNO system blackening layer 2 is expressed by the following Equation 2. R _0f is one surface reflectance of CuNO system blackening layer 2 _(%), represented by _R 0f ₌ R 0/2. As shown in FIG. 14, the single-sided reflectance R _0f of the CuNO-based blackened layer 2 is the reflectance of the reflected light 21 on the surface of the CuNO-based blackened layer 2. T _f is the transmittance (%) of the CuNO-based blackening layer 2 and is represented by T _f = T. As shown in FIG. 15, the transmittance T _f of the CuNO-based blackening layer 2 is the ratio of the intensity of the outgoing light 24 to the intensity of the incident light 20.

  When an electrode or a protective layer is formed on the substrate, or when the composition of the blackening layer is unknown, blackening is performed in the “Method for preparing measurement sample” in (A-1) above. The thickness and composition of the layer are prepared so that the thickness and composition ratio obtained by the following method (A-5) are the same. In this case, the procedure (A-2) is omitted.

By performing (A-5) film thickness measurement of the blackening layer of an unknown sample and XPS analysis section observation of an unknown sample, measuring the thickness d _u blackening layer of an unknown sample. For the measurement of the film thickness _{d u} of an unknown sample, the focused ion beam processing observation apparatus::; (manufactured by Hitachi High-Technologies Corporation SU8010 No.) (No. FB2200 manufactured by Hitachi High-Technologies Corporation), and super-resolution field emission scanning electron microscope Use.

  The component ratio of the blackened layer of the unknown sample is analyzed by an X-ray photoelectron spectrometer (XPS) to obtain the composition ratio of the blackened layer of the unknown sample. The composition ratio of the blackened layer of the unknown sample is an average value of composition ratios at arbitrary five points. The specifications of the XPS analyzer are as follows.

[Device specifications]
Product name: Quantum 2000 manufactured by ULVAC-PHI
X-ray source: mono-AlKa (hv: 1486.6 ev)
Detection depth: several to several tens of nm
Uptake accuracy: approx. 45 °
Analysis area: about 200μmφ spot

[Analysis sputtering conditions]
Ion species: Ar +
Acceleration voltage: 1 kV
Scanning range: 2x2mm
Sputtering speed: 1.5 nm / min (SiO ₂ equivalent value)

(B) Reflectivity measurement test In Table 1, “reflectance” is the reflection obtained when each sample is irradiated with visible light vertically from the blackened layer side and the wavelength of the visible light is scanned from 400 nm to 700 nm. Rate. The instrument used for the measurement of reflectance is a spectrocolorimeter (product number: CM-3500d; manufactured by KONICA MINOLTA). In this test, it was confirmed whether the reflectance was 5% or less at a wavelength of 400 nm to 700 nm.

(C) Etching controllability measurement test In Table 1, "Etching controllability" indicates that each sample is composed of a CuNO blackening layer and a Cu layer (or only a Cu layer) using an optical microscope or SEM from the blackening layer side. This was done by observing the etching shape. In this test, it is determined that the etching controllability is good if the etching shape of the end portions of the blackened layer and the Cu layer (or only the Cu layer) is linear, and the etching control is difficult if the meandering shape.

Table 1 shows the test conditions and results of this test. Sample number: Dielectric layer, blackened layer, Cu layer material; Dielectric band layer, blackened layer, Cu layer thickness (nm); Blackened layer The amount of N ₂ gas and O ₂ gas introduced during formation (%); extinction coefficient; reflectance (%); 16 to 18 are graphs showing extinction coefficients at wavelengths of 400 nm to 700 nm in Example 1 to Comparative Example 2. FIG. FIG. 19 to FIG. 27 are graphs showing the reflectances at wavelengths of 400 nm to 700 nm in Example 1 to Comparative Example 8.

Example 1
Sample 1 having a dielectric layer of SiO ₂ , a blackened layer of CuNO, and a dielectric layer and a blackened layer of 66.8 nm and 40.1 nm, respectively, was prepared. As shown in FIG. 16, the extinction coefficient k of CuNO of Sample 1 was 1.17 to 1.38 at a wavelength of 400 nm to 700 nm. Further, as shown in FIG. 19, the reflectance of Sample 1 at a wavelength of 400 nm to 700 nm was 0.4% to 4.8%. As a result of observing the SEM photograph, the edge of the blackened layer was a linear etched shape.

(Comparative Example 1)
A sample 2 having a thickness of 40 nm and having a blackened layer of CuNO was prepared without providing a dielectric layer. As shown in FIG. 17, the extinction coefficient k of CuNO of Sample 2 was 1.26 to 1.57 at wavelengths of 400 nm to 700 nm. However, as shown in FIG. 20, the reflectance of Sample 2 was 15.0% to 28.7% at wavelengths of 400 nm to 700 nm. As a result of observing the SEM photograph, the edge of the blackened layer was a linear etched shape.

(Comparative Example 2)
Sample 3 having a dielectric layer of SiO ₂ , a blackened layer of CuO, and a dielectric layer and a blackened layer of 10 nm and 39.9 nm, respectively, was prepared. As shown in FIG. 18, the extinction coefficient k of CuO of Sample 3 was 0.31 to 0.81 at wavelengths of 400 nm to 700 nm. Further, as shown in FIG. 21, the reflectance of the sample 3 was 8.0% to 16.1% at a wavelength of 400 nm to 700 nm. As a result of observing the SEM photograph, a meandering shape was observed at the end of the blackened layer.

(Comparative Example 3)
Sample 4 in which the dielectric layer and the blackening layer were not provided was prepared. Since the extinction coefficient k is a value for the blackened layer, it was not measured. As shown in FIG. 22, the reflectance of the sample 4 was 38.1% to 87.2% at a wavelength of 400 nm to 700 nm. As a result of observing the SEM photograph, the end portion of the Cu layer had a linear etching shape, which is due to the fact that only the Cu layer was formed on the substrate.

(Comparative Example 4)
A sample 5 having a thickness of 30 nm and having a blackened layer of CuO was prepared without providing a dielectric layer. As shown in FIG. 18, the extinction coefficient k of CuO of Sample 5 was 0.31 to 0.81 at wavelengths of 400 nm to 700 nm. However, as shown in FIG. 23, the reflectance of Sample 2 was 3.3% to 17.3% at wavelengths of 400 nm to 700 nm. As a result of observing the SEM photograph, a meandering shape was observed at the end of the blackened layer.

(Comparative Example 5)
A sample 6 having a thickness of 30 nm and having a blackened layer of CuN was prepared without providing a dielectric layer. As shown in FIG. 24, the reflectance of Sample 2 was 9.0% to 18.3% at a wavelength of 400 nm to 700 nm. As a result of observing the SEM photograph, a meandering shape was observed at the end of the blackened layer.

(Comparative Example 6)
Sample 7 having a dielectric layer of 170.5 nm of SiO ₂ and 29.5 nm of TiO ₂ was prepared without providing a blackening layer. The extinction coefficient k of SiO ₂ and TiO ₂ was 0. As shown in FIG. 25, the reflectance of the sample 7 was 11.5% to 89.1% at a wavelength of 400 nm to 700 nm. As a result of observing the SEM photograph, the end portion of the Cu layer was in a linear etching shape because the dielectric layer was formed after etching only Cu.

(Comparative Example 7)
A sample 8 having a dielectric layer in which a total of 8 layers of SiO ₂ and TiO ₂ were alternately laminated, a total of 8 layers, was prepared without providing a blackened layer. The extinction coefficient k of SiO ₂ and TiO ₂ was 0. As shown in FIG. 26, the reflectance of Sample 8 was 0.6% to 96.5% at a wavelength of 400 nm to 700 nm. As a result of observing the SEM photograph, the end portion of the Cu layer was in a linear etching shape because the dielectric layer was formed after etching only Cu.

(Comparative Example 8)
A sample 9 having a NiCu blackened layer with a thickness of 35 nm was prepared without providing a dielectric layer. As shown in FIG. 27, the reflectance of the sample 9 was 12.3% to 20.6% at a wavelength of 400 nm to 700 nm. As a result of observing the SEM photograph, a meandering shape was observed at the end of the blackened layer.

  From the above test results, it can be seen that if a CuNO blackening layer having a similar etching speed to that of the Cu layer is used as the blackening layer, the width of each of the Cu layer and the CuNO blackening layer becomes a linear etching shape. It was. Further, by laminating both a CuNO blackening layer and a dielectric layer having an extinction coefficient of 1.0 or more in the visible light wavelength range of 400 nm to 700 nm, the reflectance in the entire wavelength range is 5%. We concluded that we can:

1: substrate 2, 2a, 2b: Cu layer 3, 3a, 3b: CuNO blackening layer 4, 4a, 4b, 4c, 4d, 5, 5a, 5b: dielectric layer 10: resist layer 50: sputtering apparatus 51: Sealed housing 52: Substrate take-up reel 53: Substrate take-up reel 54: Partition 55: First compartment 56: Second compartment 57: Cu target material 58, 59: Inlet port 60: Pinch roll 61 : Inner drum 62: Pinch roll 63: Conductor 64: Controller 65: Low vacuum suction port 66: High vacuum suction port

Claims (9)

Forming a laminated film in which a Cu layer and a CuNO-based blackening layer are sequentially laminated on at least one main surface of the substrate;
Forming a resist layer in a predetermined region on the laminated film;
Removing the region of the laminated film that is not covered with the resist layer by bringing the laminated film into contact with an etching solution;
Forming a dielectric layer on the substrate and the laminated film patterned, and
A method of manufacturing an electrical device, wherein the CuNO blackening layer has an extinction coefficient of 1.0 to 1.8 in a wavelength range of 400 nm to 700 nm.   The method for manufacturing an electrical device according to claim 1, wherein the CuNO-based blackened layer is a CuNO blackened layer. The method for manufacturing an electric device according to claim 1, wherein the dielectric layer is a SiO ₂ layer.   The electric device according to any one of claims 1 to 3, wherein the step of forming the CuNO-based blackening layer is performed by sputtering Cu in an atmosphere containing at least nitrogen gas and oxygen gas. Manufacturing method.   The method for manufacturing an electric device according to claim 1, wherein in the step of removing a partial region of the laminated film, the laminated film is formed into a mesh pattern. A substrate;
A Cu layer and a CuNO blackening layer are sequentially laminated on at least one main surface of the substrate, and a patterned laminated film;
A dielectric layer formed on the substrate and the patterned laminated film,
An electrical device, wherein an extinction coefficient of the CuNO blackening layer at a wavelength of 400 nm to 700 nm is 1.0 or more and 1.8 or less.   The electric device according to claim 6, wherein the CuNO blackening layer is a CuNO blackening layer. The electric device according to claim 6, wherein the dielectric layer is a SiO ₂ layer.   The electrical device according to any one of claims 6 to 8, wherein a total film thickness of the CuNO-based blackening layer and the dielectric layer is 100 nm or less.