JPWO2015194587A1 - LAMINATE, ITS MANUFACTURING METHOD, AND ELECTRONIC DEVICE - Google Patents

Abstract

Provided are a laminated body with reduced glare (reflectance) due to metal-specific luster, a manufacturing method thereof, and an electronic device. The laminate 1 includes a transparent substrate, a metal layer 20 formed on the substrate, and metal compound layers 30a and 30b formed on at least one surface of the metal layer 20 so as to be in contact with the surface. The metal layer 20 includes at least one layer of a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm, or an alloy containing metal as a main component, and has a specific resistance of 10 μΩ · cm or less. The compound layers 30a and 30b are made of a mixture of a transparent oxide semiconductor material and at least one metal having an oxide generation free energy equivalent to or higher than that of zinc (Zn).

Description

  The present invention relates to a laminate comprising a metal and a conductive metal compound that can be used for a metal electrode for an electronic device and an optical device, and a method for manufacturing the same, and an electronic device.

  In recent years, in electrodes (including auxiliary electrodes that increase conductivity) used in various electronic devices using liquid crystal, organic EL, etc., particularly large-sized touch sensors, which are input / output devices installed on the front surface of display elements, etc. Is progressing. Among the detection electrodes, wiring electrodes, and connection electrodes included in the touch sensor (panel), particularly in the detection electrodes, when the touch sensor is increased in size, the resistance component increases, and thus a lower resistance electrode has been required. .

Conventionally, the visibility of a display has been ensured by using a conductive metal oxide having high transparency such as an oxide semiconductor mainly composed of In, Zn, Sn, Ti, or the like for an electrode for a touch panel. However, conductive metal oxides with high transparency have a limit in reducing the resistance value, and it is difficult to achieve the low resistance level required in recent years. Therefore, as an alternative material, there is a demand for practical use of a low resistance metal that can ensure visibility by micropatterning.
And in an electronic device in which a substrate with an electrode is arranged on the front surface of a display element such as a touch panel, it is a necessary condition that the visibility of display is not hindered. Only less is required.
However, if the conventional electrode made of a conductive metal oxide is simply replaced with metal, glare occurs due to the high reflectivity specific to the metal, and thus the reflectivity needs to be lowered. In addition, it is important to configure the conductor as low as possible and electrically connectable.

  Metals with low reflectivity include molybdenum (Mo), chromium (Cr), titanium (Ti), tantalum (Ta), tungsten (W) and their alloys, but these metals are classified as having high resistance values. Applicable. In contrast, silver (Ag), aluminum (Al), copper (Cu), and the like and alloys thereof have a low resistance value but a high reflectance.

A method of laminating a metal having a high resistance value and a low reflectance on a metal having a low resistance value and a high reflectance using the characteristics of these metals has been proposed. There are limits to the reduction.
Further, even if the reflectance can be reduced to some extent by stacking the metals, the etching rates of the respective metals are different from each other. Therefore, it is particularly difficult to finely process each layer in a wet etching process. Moreover, if it adjusts so that a wet etching process can be implemented favorably, conversely, sufficient reduction of a reflectance will become difficult.

  Therefore, as a method for reducing the reflectance, a method of forming a dielectric layer, a metal oxide, a metal nitride, a metal oxynitride, or a metal carbide layer on the metal layer to form a two-layer or three-layer structure, A method of forming a dielectric, a metal oxide, a metal nitride, a metal oxynitride, or a metal carbide layer after a low-reflectance metal semi-transmissive film is disposed on the metal layer has been proposed ( For example, Patent Documents 1 to 7).

That is, Patent Document 1 discloses a laminate in which a blackening layer made of copper nitride and oxygen is formed on a base material as an electromagnetic wave prevention film functional film for a plasma display, and touch panel by means of metallic gloss reflected light of a wiring portion. A transparent conductive film that does not deteriorate the visibility of the display disposed below is disclosed.
Patent Document 2 discloses a film-like touch panel sensor that suppresses reflection from a wiring by forming a black copper oxide film on the viewing side of a striped or mesh-shaped copper wiring provided on the film. Yes.
In Patent Document 3, a sensor electrode made of a metal material and an absorption layer also serving as an adhesion layer made of an inorganic oxide material formed on the sensor electrode are formed on an insulating base material, thereby achieving high definition. A touch panel sensor that can be etched and has a low resistance is disclosed.
Patent Document 4 discloses at least one selected from the group consisting of a dielectric substance, a metal, a metal alloy, a metal oxide, a metal nitride, a metal oxynitride, and a metal carbide on a transparent substrate. By laminating an absorption layer, which is a blackening layer, and a conductive layer containing at least one selected from Ni, Mo, Ti, Cr, Al, Cu, Fe, Co, V, Au, and Ag, It has been disclosed to improve the visibility of the layer and the reflection properties with respect to external light.
Patent Document 5 discloses that a blackened layer made of copper, nickel, and oxygen is provided on the transparent resin substrate side of a conductor layer made of a copper plating layer. Patent Document 6 discloses a blackened layer, a metal It is disclosed in Patent Document 7 that a layer, a substrate, a blackened layer, and a metal layer are provided in this order, and the blackened layer is made of copper nitride, thereby suppressing a reduction in visibility of the display due to metallic glossy reflected light. Discloses that a Ni—Zn film is used for the metal layer and a Cu film is used for the conductive layer.
As described above, in Patent Documents 1 to 7, as a material for forming the absorption layer, a high refractive index transparent thin film, a transparent conductive film, a functional transparent layer, a metal oxide, a metal nitride, a metal oxynitride, a dielectric Substances etc. are disclosed.
According to the methods of Patent Documents 1 to 7 and the like, the reflection by metal can be absorbed by the blackening layer or the absorption layer, and the reflectance can be further reduced by repeatedly laminating a plurality of layers.

JP 2013-169712 A JP 2013-206315 A JP 2013-149196 A Special table 2013-540331 gazette JP 2008-311565 A JP2013-129183A JP 2007-307661 A

However, the materials used for the absorption layer or blackening layer of Patent Documents 1 to 7 have a refractive index (n) in the visible range of about 1.4 to 2.5 and an extinction coefficient (k) of 0. The absorption layer or blackening layer is a transparent thin film or layer with little absorption because of .01 to 0.25.
Therefore, even if the absorption layer or blackening layer of Patent Documents 1 to 7 is laminated on the surface of the metal layer for the purpose of reducing the reflectance in the visible range, the maximum or minimum reflectance in the visible range is caused by light interference. Occurs, interference color is generated, and the effect of reducing reflectivity as expected is not obtained.

Moreover, in patent documents 1-7, since each layer is laminated | stacked repeatedly, the difference of the etching rate of each layer becomes large, and a restriction | limiting arises in a selection substance.
Since the absorption layer or blackening layer of Patent Documents 1 to 7 is a metal compound thin film, it cannot be etched together with the metal layer in the patterning process, and an etchant different from the metal layer is required or can be etched. Even so, the etching rate of the metal layer and the metal compound layer cannot be matched, and one of the films in the laminated structure is overetched or underetched, so that a fine pattern cannot be formed as expected. The phenomenon occurs.

  In addition, when a metal compound other than a transparent conductive film that is a transparent oxide semiconductor material is used as the absorption layer or the blackening layer, depending on the presence or value of the conductivity of the absorption layer or the blackening layer, other connection electrodes and There are cases where it is necessary to increase the number of steps for connection or to change the film configuration, and there are limitations when used as electrodes.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a laminate, a method of manufacturing the same, and an electronic apparatus that reduce glare (reflectance) due to gloss inherent to metal. .
Another object of the present invention is to reduce the metal reflectivity in the visible range to a flat reflectivity as much as possible to make it a blackened color tone, and perform wet etching all at once even in a layered state. It is an object of the present invention to provide a laminate including an optimal absorption layer having conductivity corresponding to a low-resistance metal layer, a manufacturing method thereof, and an electronic device.

  According to the laminate of the present invention, the subject is a transparent substrate, a metal layer formed on the substrate, and a metal formed on at least one surface of the metal layer so as to be in contact with the surface. A laminate comprising a compound layer, wherein the metal layer includes at least one layer of a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm, or an alloy containing the metal as a main component, and has a specific resistance of 10 μΩ. The metal compound layer is made of a mixture of a transparent oxide semiconductor material and at least one metal having an oxide generation free energy equivalent to or higher than that of zinc (Zn). It is solved by.

Since it is configured in this manner, it is possible to arbitrarily combine a transparent oxide semiconductor material having conductivity and a metal having an oxide generation free energy equal to or higher than that of zinc (Zn), and electrical characteristics (conductivity ), Optical characteristics (refractive index and extinction coefficient) and etching characteristics (solubility in etchant, etching rate) can be freely controlled so as to have desired values.
Therefore, electrical wiring connection to other metal wiring is easy, while ensuring good conductivity, reducing the metal surface reflectance from the viewing side and blackening, thereby suppressing glare caused by the metal layer It is possible to achieve a conductive laminate capable of forming an arbitrary fine pattern at once by wet etching with a small number of layer structures.
When the laminate of the present invention is used as an electrode material for an electronic device, the response speed can be improved, the visibility is improved by microfabrication and reflectance reduction, the patterning is formed by batch etching, and the minimum layer configuration As a result, productivity can be improved and cost can be reduced.

Moreover, since the metal compound layer is made of a mixture of a transparent oxide semiconductor material and a metal having an oxide generation free energy equivalent to or higher than that of zinc (Zn), the optical constant (refractive index) is ensured after ensuring conductivity. , Extinction coefficient and absorption) can be optimized, and the laminate can be easily designed. Moreover, the laminated body provided with the light absorption layer which has favorable electroconductivity is obtained.
In addition, compared to the case of being composed only of compounds such as metal oxides, metal nitrides, metal oxynitrides, metal carbides, etc., it is a layer having a large absorption, so that the reflectance of the metal layer surface can be greatly reduced, Even in the case of a two-layer configuration including only one layer and one metal compound layer, glare of the laminate is reduced, and visibility is improved when the laminate of the present invention is used for a display or the like.
Since the visibility is improved, the laminate of the present invention can be suitably used for various display elements, touch panels, and other devices that require aesthetic appearance, such as display devices, light emitting elements, and touch panels. It can be used as an electrode for solar cells and other electronic devices.

Further, the metal layer includes at least one layer of a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm, or an alloy containing the metal as a main component, and a specific resistance is 10 μΩ · cm or less. Since a low resistance metal is used for the metal layer, when the wiring pattern is formed from the metal layer and the metal compound layer, the wiring pattern can be thinned. Can be maintained.
In the wet etching process, the laminate of the present invention can form a pattern of the metal layer and the metal compound layer or the metal compound layer, the metal layer, and the metal compound layer at once, and a fine pattern of 4 μm is also possible. Therefore, it performs a good function as a main electrode such as a touch panel, a display element, a light emitting element, a photoelectric conversion element, an auxiliary electrode, and a connection electrode with a terminal.

A metal having an oxide generation free energy equal to or higher than that of zinc (Zn) is a metal that can secure conductivity and is difficult to oxidize. Therefore, by mixing the metal compound layer with a metal having an oxide generation free energy equal to or higher than that of zinc (Zn), the property that the metal that is difficult to oxidize has high absorption can be effectively used.
Moreover, since not only the metal layer but also the metal compound layer is conductive, it can be easily electrically connected to other wirings, and a wiring pattern is formed from the metal layer and the metal compound layer of the present invention. It can be used.

In this case, the metal layer may be formed by laminating the at least one alloy layer and a dissimilar metal layer made of a metal different from the metal that is a main component of the alloy layer. .
With this configuration, it is easy to adjust characteristics such as the optical constant and etching rate of the laminate.

At this time, the metal layer includes a single layer made of copper (Cu), aluminum (Al), silver (Ag), or an alloy of these metals, a molybdenum (Mo) layer, a molybdenum alloy layer, and aluminum (Al). Two layers or three layers selected from the group consisting of a layer and an aluminum alloy layer may be laminated.
Since it is configured in this way, the resistance of the metal layer can be reduced, and when the wiring pattern is formed from the metal layer and the metal compound layer, the wiring pattern can be thinned. Visibility can be maintained.

At this time, the metal compound layer may have a refractive index (n) in the visible range (400 to 700 nm) of 2.0 to 2.8 and an extinction coefficient (k) of 0.6 to 1.6. .
Since it comprises in this way, reflection can be suppressed and the dark black laminated body without redness, yellowishness, blueness, etc. can be comprised.

At this time, the metal compound layer is made of indium oxide (In ₂ O ₃ ), zinc oxide (ZnO) or tin oxide (SnO ₂ ), or indium oxide (In ₂ O ₃ ), zinc oxide (ZnO) or tin oxide. It consists of a layer composed of a mixture of one or two kinds of transparent oxide semiconductor materials containing (SnO ₂ ) as a main component and containing an additive, and a metal having an oxide generation free energy equal to or higher than that of zinc (Zn). May be.
Since it is configured in this way, it becomes possible to construct a dark black laminate without redness, yellowness, blueness, etc., with a small average reflectance in the visible range and a difference between the maximum reflectance and the minimum reflectance. .
In addition, when two types of transparent oxide semiconductor materials are used for the metal compound layer, a wide range of optical constants, etching rates, etc. of the laminate can be selected by changing the ratio of the two types of transparent oxide semiconductor materials. Can do.

At this time, the metal having an oxide generation free energy equivalent to or higher than that of zinc (Zn) is zinc (Zn), copper (Cu), nickel (Ni), molybdenum (Mo), cobalt (Co), lead (Pb). ), Any one or more metals selected from the group including molybdenum alloys.
As described above, since these metals that can ensure conductivity and are not easily oxidized are added to the metal compound layer, the absorption of the metal compound layer can be increased, and the reflectance of the laminate can be reduced.

At this time, the metal compound layer is formed by mixing the transparent oxide semiconductor material and a metal having oxide generation free energy equal to or higher than zinc (Zn) at a volume ratio of 8: 2 to 5: 5. May be.
With this configuration, it is possible to optimize the optical constants (refractive index, extinction coefficient, and absorption) while ensuring conductivity, and the average reflectance and maximum reflectance in the visible range. Thus, it is possible to construct a dark black laminate having a small difference in minimum reflectance and having no redness, yellowness, blueness or the like.

At this time, the metal compound layer contains one or more of the group consisting of oxygen (O), nitrogen (N), and carbon (C), and the film thickness of the metal compound layer ranges from 30 nm to 60 nm. It may be.
Because of this structure, the optical constants (refractive index, extinction coefficient, absorption) of the metal compound layer constituting the laminate are appropriately adjusted by adjusting the amount of nitrogen, oxygen or carbon in the metal compound layer. Can be controlled. Further, nitrogen, oxygen, or carbon in the metal compound layer has a function of adjusting conductivity and etching characteristics (etching rate), so that it can be adjusted to an optimum film quality electrically, optically, and chemically. In addition, the reactive gas to be included broadens the range in which etching characteristics and optical characteristics can be adjusted, and more types of metals and transparent oxide semiconductor materials can be used for the metal compound layer. Moreover, it becomes possible to make the laminated body of a metal compound layer and a metal layer into a fine pattern.
Furthermore, when the metal compound layer is formed on the surface of the metal layer on the opposite side of the substrate, the surface of the laminate is covered with a conductive material made of metal nitride, oxide, or carbide. It can be set as the laminated body excellent in tolerance.

In addition, a transparent oxide semiconductor material having conductivity, a metal having an oxide free energy equal to or higher than zinc (Zn), and one of oxygen (O), nitrogen (N), and carbon (C) The above can be arbitrarily combined, and electrical characteristics (conductivity), optical characteristics (refractive index and extinction coefficient), and etching characteristics (solubility in etchant, etching rate) can be freely set to desired values. Control becomes possible.
Therefore, the electrical wiring connection to other metal wiring is easy, and the glare caused by reducing the metal surface reflectivity from the viewing side (low reflectivity and blackening) while ensuring good conductivity. In addition, a conductive laminate that can form an arbitrary fine pattern in a batch by wet etching can be secured with a small number of layers.
When the laminate of the present invention is used as an electrode material for an electronic device, the response speed can be improved, the visibility is improved by microfabrication and reflectance reduction, the patterning is formed by batch etching, and the minimum layer configuration As a result, productivity can be improved and cost can be reduced.

At this time, in the visible region (400 to 700 nm), the reflectance with respect to light incident from the metal compound layer side of the laminate is an average of 1.0% or more and 15% or less, and the difference between the maximum reflectance and the minimum reflectance. Is 10% or less, and may be visually dark.
Since it comprises in this way, the glare of a laminated body is reduced and visibility improves when the laminated body of this invention is used for a display etc.
Since the visibility is improved, the laminate of the present invention can be suitably used for various display elements, touch panels, and other devices that require aesthetic appearance, such as display devices, light emitting elements, and touch panels. It can be used as an electrode for solar cells and other electronic devices.
In order for the laminate to exhibit a darker black color, it is important to select a material in which the difference between the maximum reflectance and the minimum reflectance is as small as possible. In the present invention, the maximum reflectance and the minimum reflectance Therefore, a good dark black laminate can be obtained.

At this time, at least a part of the metal layer and the metal compound layer formed on the at least one surface of the metal layer so as to be in contact with the surface includes the laminate of the present invention. Or may be formed into a pattern.
Since it is configured in this manner, the laminate of the present invention can be suitably used for various display elements, touch panels, and other devices that require aesthetic appearance, such as display devices, light-emitting elements, It can be used as an electrode for touch panels, solar cells, and other electronic devices.

  According to the method for producing a laminate of the present invention, at least one layer of a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm or an alloy containing the metal as a main component is provided on the transparent substrate. At least one of a metal layer forming step of forming a layer and forming a metal layer having a specific resistance of 10 μΩ · cm or less, and before and after the metal layer forming step, a transparent oxide semiconductor material, zinc ( A metal compound layer forming step of forming a metal compound layer, which is a light absorption layer having conductivity, by forming a film of a mixture of at least one kind of metal having an oxide generation free energy equivalent to or greater than (Zn). It is solved by doing.

Since the metal compound layer is made of a mixture of a transparent oxide semiconductor material and a metal having an oxide generation free energy equal to or higher than that of zinc (Zn), the optical constant (refractive index, extinction) is ensured while ensuring conductivity. It is possible to optimize the attenuation coefficient and absorption), and the laminate can be easily designed.
In addition, compared to the case of being composed only of compounds such as metal oxides, metal nitrides, metal oxynitrides, metal carbides, etc., it becomes a layer having a large absorption, so that the reflectance on the surface of the metal layer can be greatly reduced. Even in the case of a two-layer configuration including only one layer and one metal compound layer, glare of the laminate is reduced, and visibility is improved when the laminate of the present invention is used for a display or the like.
Since the visibility is improved, the laminate of the present invention can be suitably used for various display elements, touch panels, and other devices that require aesthetic appearance, such as display devices, light emitting elements, and touch panels. It can be used as an electrode for solar cells and other electronic devices.

  Further, the metal layer includes at least one layer of a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm, or an alloy containing the metal as a main component, and a specific resistance is 10 μΩ · cm or less. Since a low resistance metal is used for the metal layer, when the wiring pattern is formed from the metal layer and the metal compound layer, the wiring pattern can be thinned. Can be maintained.

According to the present invention, a transparent oxide semiconductor material having conductivity and at least one kind of metal having an oxide generation free energy equivalent to or higher than that of zinc (Zn) can be arbitrarily combined, and electrical characteristics ( Conductivity), optical characteristics (refractive index and extinction coefficient), and etching characteristics (solubility in etchant, etching rate) can be freely controlled to have desired values.
Therefore, electrical wiring connection to other metal wiring is easy, while ensuring good conductivity, reducing the metal surface reflectance from the viewing side and blackening, thereby suppressing glare caused by the metal layer It is possible to achieve a conductive laminate capable of forming an arbitrary fine pattern at once by wet etching with a small number of layer structures.
When the laminate of the present invention is used as an electrode material for an electronic device, the response speed can be improved, the visibility is improved by microfabrication and reflectance reduction, the patterning is formed by batch etching, and the minimum layer configuration As a result, productivity can be improved and cost can be reduced.

1 is a schematic cross-sectional view of a laminate 1 according to an embodiment of the present invention. In Examples 1-4 which changed the ratio of ZnO and Cu and formed the metal compound layer, it is a graph which shows the measured value of the refractive index in 400-700 nm of the board | substrate with which the metal compound layer was formed. It is a graph which shows the calculated value of the extinction coefficient of the board | substrate with a metal compound layer of Examples 1-4 which changed the ratio of ZnO and Cu and formed the metal compound layer into a film. It is a graph which shows the measured value of the reflectance of the laminated body of Examples 1-4 which changed the ratio of ZnO and Cu into a metal compound layer, and formed the metal layer which consists of Cu. It shows the difference between the average reflectance and the maximum reflectance and the minimum reflectance of the laminates of Examples 1 to 4, in which the metal compound layer was formed by changing the ratio of ZnO and Cu, and then the metal layer made of Cu was formed. It is a graph. It is a graph which shows the refractive index of the board | substrate with a metal compound layer of Examples 5-14 which changed into nitrogen or oxygen introduction amount, and formed the Zn-Cu (5: 5) metal compound layer into a film. It is a graph which shows the extinction coefficient of the board | substrate with a metal compound layer of Examples 5-14 which changed into nitrogen or oxygen introduction amount and formed the Zn-Cu (5: 5) metal compound layer into a film. The graph which shows the measured value of the reflectance of the laminated body of Examples 5-14 which formed the metal layer which forms a Zn-Cu (5: 5) metal compound layer by changing nitrogen or oxygen introduction amount, and formed the metal layer which consists of Cu It is. The average reflectance and the maximum reflectance of the laminates of Examples 5 to 14, in which the Zn—Cu (5: 5) metal compound layer was formed by changing the amount of nitrogen or oxygen introduced, and then the Cu metal layer was formed. It is a graph which shows the difference of the minimum reflectance. In ₂ O ₃ and by changing the ratio of Mo after forming a metal compound layer is a graph showing measured values of reflectivity of the laminate of Example 15 to 19 was formed a metal layer made of Cu. After changing the ratio of In ₂ O ₃ and Mo to form a metal compound layer, the average reflectivity and the difference between the maximum reflectivity and the minimum reflectivity of the laminates of Examples 15 to 19 in which the metal layer made of Cu was formed It is a graph which shows. Is a graph showing the measurement value of the reflectance of the laminate of the ZnO-Cu and In ₂ O ₃ by changing the ratio of post-forming a metal compound layer, Examples 21 to 25 was formed a metal layer made of Cu . The average reflectance, the maximum reflectance, and the minimum reflectance of the laminates of Examples 21 to 25 in which the metal compound layer was formed by changing the ratio of ZnO—Cu and In ₂ O ₃ and then the metal layer made of Cu was formed. It is a graph which shows the difference of a rate. By changing the ratio between ZnO-Cu and SnO ₂ after forming a metal compound layer is a graph showing measured values of reflectivity of the laminate of Example 26 to 30 was deposited a metal layer made of Cu. After changing the ratio of ZnO—Cu and SnO ₂ to form a metal compound layer, the average reflectance and the maximum reflectance and the minimum reflectance of the laminates of Examples 26 to 30 in which the metal layer made of Cu was formed. It is a graph which shows a difference. By changing the amount of nitrogen introduced after forming a metal compound layer of ZnO-Cu and SnO _2, it is a graph showing measured values of reflectivity of the laminate of Example 31 to 36 was formed a metal layer made of Cu. The average reflectance, the maximum reflectance, and the minimum reflectance of the laminates of Examples 31 to 36, in which the metal compound layer of ZnO—Cu and SnO ₂ was formed after changing the nitrogen introduction amount, and then the metal layer made of Cu was formed. It is a graph which shows the difference of. The measured values of the reflectance of the laminates of Examples 37 to 41 in which the metal compound layer of ZnO and Cu was formed by changing the amount of nitrogen introduced, and then the metal layer of the two-layer structure of the MoNb film and the AlNd film was formed are shown. It is a graph. The average reflectance and the maximum reflectance of the laminates of Examples 37 to 41 in which the metal compound layer of ZnO and Cu was formed by changing the amount of nitrogen introduced, and then the metal layer having the two-layer structure of the MoNb film and the AlNd film was formed. It is a graph which shows the difference of minimum reflectance. It is a graph which shows the measured value of the reflectance of the laminated body of Examples 42-47 which formed the metal layer which changed the film thickness and formed the metal layer which consists of an AlNd film | membrane or an APC film | membrane after forming the metal compound layer of ZnO and Cu. The average reflectance, the maximum reflectance, and the minimum reflectance of the laminates of Examples 42 to 47 in which the metal compound layer of ZnO and Cu was formed after changing the film thickness, and then the metal layer composed of the AlNd film or the APC film was formed. It is a graph which shows the difference of. After forming a metal compound layer in which the ZnO ratio is changed to 1 to 5 with respect to two kinds of metals (Ni: Cu = 1: 1) having an oxide generation free energy equivalent to or higher than that of Zn, Cu is used. It is a graph which shows the difference of the average reflectance of the laminated body of Example 54-58 formed into a film, and the difference of the maximum reflectance and minimum reflectance. The average reflectance, maximum reflectance, and minimum reflectance of the laminates of Examples 54, 59, and 60 in which the oxygen flow rate during the formation of the metal compound layer with Ni: Cu: ZnO = 1: 1: 1 was changed. It is a graph which shows a difference. It is a graph which shows the measured value of the reflectance of the laminated body in Examples 54-60 of FIG.22 and FIG.23. The ratio of one kind of metal (Mo) and oxide (ZnO + Al ₂ O ₃ ) is 1: 2, and the ratio of ZnO to Al ₂ O ₃ is (5: 1), (4.5: 1.5), ( It is a graph which shows the difference of the average reflectance of the laminated body of Examples 61-63 which varied into 4: 2), and formed the metal compound layer into 50 nm, and the difference of the maximum reflectance and the minimum reflectance. The ratio of one kind of metal (Mo) and oxide (ZnO + Al ₂ O ₃ ) is 1: 2, and the ratio of ZnO to Al ₂ O ₃ is (5: 1), (4.5: 1.5), ( It is a graph which shows the measured value of the reflectance of the laminated body of Examples 61-63 which varied by 4: 2) and formed the metal compound layer into 50 nm. ZnO: An implementation in which a metal layer made of Cu or Al was formed after forming a metal compound layer (50 nm) with a ratio of one kind of metal (Mo): Al ₂ O ₃ of 4.5: 3: 1.5. It is a graph which shows the difference of the average reflectance of the laminated body of Examples 64 and 65, and the difference of the maximum reflectance and minimum reflectance. ZnO: An implementation in which a metal layer made of Cu or Al was formed after forming a metal compound layer (50 nm) with a ratio of one kind of metal (Mo): Al ₂ O ₃ of 4.5: 3: 1.5. It is a graph which shows the measured value of the reflectance of the laminated body of Examples 64 and 65. ZnO: After forming a metal compound layer (in increments of 5 nm between 40 nm and 60 nm) at a ratio of one kind of metal (Mo): Al ₂ O ₃ of 4.5: 3: 1.5, an AlNd alloy as a metal layer It is a graph which shows the difference of the average reflectance of the laminated body of Examples 66-70 which formed into a film the metal layer (100 nm) which consists of, and the maximum reflectance and minimum reflectance. ZnO: After forming a metal compound layer (in increments of 5 nm between 40 nm and 60 nm) at a ratio of one kind of metal (Mo): Al ₂ O ₃ of 4.5: 3: 1.5, an AlNd alloy as a metal layer It is a graph which shows the measured value of the reflectance of the laminated body of Examples 66-70 which formed into a film the metal layer (100 nm) which consists of. The ratio of ZnO: Cu = 1: 1 and Al ₂ O ₃ is set to (ZnO: Cu) :( Al ₂ O ₃ ) = 10: 3.5 to form a metal compound layer (in increments of 15 nm between 35 nm and 65 nm). It is a graph which shows the difference of the average reflectance of the laminated body of Examples 71-73 which film-formed Cu as a metal layer after film | membrane, and the maximum reflectance, and the minimum reflectance. The ratio of ZnO: Cu = 1: 1 and Al ₂ O ₃ is set to (ZnO: Cu) :( Al ₂ O ₃ ) = 10: 3.5 to form a metal compound layer (in increments of 15 nm between 35 nm and 65 nm). It is a graph which shows the measured value of the reflectance of the laminated body of Examples 71-73 which formed Cu into a film as a metal layer after film | membrane.

Hereinafter, the laminated body concerning one Embodiment of this invention is demonstrated in detail using drawing.
<Configuration of Laminate 1>
The laminated body 1 of the present embodiment is a touch panel of a display device such as a liquid crystal display or a plasma display incorporated in various electronic devices such as a mobile phone, a portable information terminal, a game machine, a ticket vending machine, an ATM device, and a car navigation system. Used as a substrate with electrodes. In addition, it can also be used as a main electrode such as a display element, a light emitting element, a photoelectric conversion element, an auxiliary electrode, and a terminal connection electrode.
As shown in FIG. 1, the laminate 1 of the present embodiment is formed by sequentially forming a metal compound layer 30 a, a metal layer 20, and a metal compound layer 30 b on a transparent substrate 10.
However, you may comprise the laminated body 1 of this embodiment so that the metal compound layer 30b may not be provided by the application used. In this case, the metal layer 20 is formed on the transparent substrate 10, and the conductive metal compound layer 30 a that is a metal compound layer is formed between the transparent substrate 10 and the metal layer 20.
In addition, the laminate 1 of the present embodiment is configured not to include the metal compound layer 30 a, the metal layer 20 is directly formed on the transparent substrate 10, and the metal compound layer 30 b is formed on the metal layer 20. It may be.

The substrate 10 is a known transparent substrate, made of a transparent glass material, a transparent resin, or the like, and may be a transparent resin film.
The metal layer 20 includes one or more layers of a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm or an alloy mainly composed of a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm. .
As the metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm, for example, a single metal such as silver (Ag), copper (Cu), or aluminum (Al) is used. Since the laminate 1 is used as an electrode, a metal substance that has a low resistance value and can be freely patterned is used as a material for the metal layer 20 except when a high resistance value is specified and used. This is because it is preferable.

Moreover, the metal layer 20 may be comprised from metal alloys, such as Ag, Cu, and Al.
Although the conductivity is slightly inferior, molybdenum (Mo), nickel (Ni) or an alloy thereof is used as a material for the metal layer 20 in order to efficiently reduce the reflectance in combination with the metal compound layers 30a and 30b. Etc. may be used.

However, in consideration of conductivity and etching properties, Cu is a more effective material in terms of conductivity and etching properties when used for the metal layer 20.
The metal layer 20 is adjusted so that the specific resistance of the entire layer is 10 μΩ · cm or less.
The metal layer 20 includes one layer made of a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm, such as Ag, Cu, or Al, or an alloy thereof, and a dissimilar metal layer made of a metal different from the metal constituting one layer. And may be laminated. For example, one layer made of a metal of Ag, Cu, Al or an alloy thereof, and this one layer includes a different metal, and a layer made of any one of Mo, Mo alloy, Al, Al alloy is laminated 2 It may consist of more than one layer.

The metal compound layers 30a and 30b of the present embodiment are made of a mixture of a transparent oxide semiconductor material and at least one metal having an oxide generation free energy equivalent to or higher than that of zinc (Zn), and has conductivity. It is a light absorption layer.
The transparent oxide semiconductor material may be indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), or any one of the main components including additives such as Sn or 2 Even if a transparent oxide semiconductor material of a kind or a dielectric or metal oxide, metal nitride, metal oxynitride, metal carbide, etc. having the same refractive index (n) 1.7 to 2.7 is used. good. However, since the metal compound layers 30a and 30b require conductivity, a transparent oxide semiconductor material may be used.

Metals having an oxide generation free energy equivalent to or higher than that of zinc (Zn) include copper (Cu), nickel (Ni), molybdenum (Mo), cobalt (Co), lead (Pb), etc., and the horizontal axis represents temperature. In the Elingham diagram of a general oxide in which the vertical axis represents the standard free energy of formation of the oxide, a metal equivalent to Cu or located above Cu can be selected.
The metal mixed in the metal compound layers 30a and 30b is a metal having an oxide generation free energy equivalent to or higher than that of zinc (Zn). When a thin film is formed by mixing with a semiconductor material, it reacts too much with oxygen and acts only as a mere additive of the transparent oxide semiconductor material to obtain a thin film having a desired optical constant with a large absorption. Because it becomes difficult.

Moreover, the reason why the metal having oxide generation free energy equal to or higher than that of zinc (Zn) is mixed in the metal compound layers 30a and 30b is as follows.
That is, the metal layer 20 is a layer that ensures main conductivity, and the metal compound layers 30 a and 30 b are layers that reduce glare due to gloss caused by the high reflectance of the metal layer 20. Accordingly, it is necessary for the metal compound layers 30a and 30b to appropriately absorb metal reflection. In the case where the metal compound layers 30a and 30b are composed of only a transparent oxide semiconductor material, a dielectric, and various metal compounds, the absorption reduction effect is not sufficiently obtained with these materials, and thus the effect of reducing the reflectivity cannot be sufficiently obtained. In this case, since the metal compound layers 30a and 30b are not sufficient, a metal semi-transmissive layer is separately disposed between the metal layer 20 and the metal compound layers 30a and 30b. It becomes necessary to alternately and repeatedly stack compound layers.

  In addition, the metal compound layers 30a and 30b made of only a transparent oxide semiconductor material, a dielectric, and various metal compounds can be reduced in reflectivity and visible only by controlling the temperature, pressure, rate, plasma, reaction gas, and the like during film formation. Any of the flatness, conductivity, and etching properties of the spectral characteristics of the region is not as expected, and it cannot be a layered product having a sufficient function.

Therefore, in the present embodiment, the metal compound layers 30a and 30b are mixed with a metal having an oxide generation free energy equivalent to or higher than that of zinc (Zn), thereby reducing reflectivity, flatness of spectral characteristics in the visible region, It has become possible to obtain sufficient performance in all of conductivity and etching properties. Accordingly, a metal semi-transmissive layer is not required.
The metal compound layers 30a and 30b of the present embodiment have a refractive index (n) in the visible range (400 to 700 nm) of 1.5 to 3.0 and an extinction coefficient (k) of 0.30 to 2.5. The absorption (α) when the film thickness is 30 to 60 nm is in the range of 20 to 60%.
In order to reduce the reflectivity and at the same time to visually darken, the change in the spectral reflectivity in the visible region is reduced, that is, the vertical axis is the spectral reflectivity and the horizontal axis is the wavelength. Therefore, it is necessary to make the shape of the graph in the visible range as flat as possible and to reduce the reflectance in the entire visible range.

  In the metal compound layers 30a and 30b, the volume ratio between the transparent oxide semiconductor material and a metal having an oxide generation free energy equal to or higher than that of zinc (Zn) is equal to or higher than that of the transparent oxide semiconductor material: zinc (Zn). The metal having free energy for oxide formation is in the range of 8: 2 to 5: 5. Thereby, all the electroconductivity of the metal compound layers 30a and 30b, an optical constant, and etching property can be made into a suitable range.

  In addition, by using a mixture of two types of transparent oxide semiconductor materials, or by using a mixture of two types of metals having an oxide generation free energy equivalent to or higher than that of zinc (Zn), the combination of materials can be changed. Since it becomes abundant, it becomes possible to finely control reflectivity, etching property, and conductivity.

Furthermore, the metal compound layers 30a and 30b are made conductive by introducing one or more reaction gases of oxygen (O ₂ ), nitrogen (N ₂ ), and carbon dioxide (CO ₂ ) during film formation. A film having good etching property can be obtained.
Further, by selecting a combination of an optical constant and a film thickness, the reflectance with respect to light incident from the metal compound layers 30a and 30b side of the laminate 1 has a visible region average of 1.0% to 15% and a maximum reflectance. And the difference between the minimum reflectance and 10% or less, it is possible to form a laminate 1 that visually shows a dark color.

<The manufacturing method of the laminated body 1>
In the laminate 1 of this embodiment, at least one layer of a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm or an alloy containing the metal as a main component is formed on a transparent substrate 10. At least one of the metal layer forming step for forming the metal layer 20 having a resistance of 10 μΩ · cm or less, and before and after the metal layer forming step, is equal to or more than the transparent oxide semiconductor material and zinc (Zn). A metal compound layer forming step for forming a metal compound layer 30a, 30b, which is a light absorption layer having conductivity, by forming a film with a mixture of at least one kind of metal having free oxide generation energy Manufactured by.
Hereinafter, the manufacturing method of the laminated body 1 of this embodiment is demonstrated.
First, a metal compound that forms a metal compound layer 30a, which is a light absorption layer having conductivity, made of a mixture of a transparent oxide semiconductor material and a metal having an oxide generation free energy equal to or higher than that of zinc (Zn) A layer forming step is performed.
In this step, a target bonded with a transparent oxide semiconductor material, a target bonded with a metal having an oxide generation energy equal to or higher than zinc (Zn), and a transparent substrate 10 are set in a sputtering apparatus, and transparent oxidation is performed. Transparent oxide semiconductor material is bonded so that the volume ratio in the film of the oxide semiconductor material and the metal having oxide generation energy equal to or higher than zinc (Zn) is in the range of 8: 2 to 5: 5 The input power of the target and the target bonded with a metal having an oxide generation energy equal to or higher than that of zinc (Zn) are adjusted, and the metal compound layer 30a is formed into a two-source film by sputtering.

  At this time, a single target in which a transparent oxide semiconductor material and a metal having an oxide generation energy equal to or higher than that of zinc (Zn) are previously mixed in a volume ratio of 8: 2 to 5: 5. Or a target in which a transparent oxide semiconductor material and a metal having an oxide generation energy equal to or higher than that of zinc (Zn) are mixed at a volume ratio of 8: 2 to 5: 5. Two-source film formation may be performed using another transparent oxide semiconductor material and / or a metal target having an oxide generation energy equal to or higher than that of zinc (Zn).

Next, a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm or a metal layer having a specific resistance of 10 μΩ · cm or less is formed by forming at least one layer of a metal having a specific resistance of 10 μΩ · cm or an alloy containing the metal as a main component. A layer forming step is performed.
In this step, a 1.0 μΩ · cm to 10 μΩ · cm metal or an alloy containing the metal as a main component is formed by sputtering by a known method so as to have a film thickness of about 120 nm. In addition, a metal having a thickness of 1.0 μΩ · cm to 10 μΩ · cm or an alloy containing the metal as a main component is sputtered by a known method to form another metal having a thickness of 1.0 μΩ · cm to 10 μΩ · cm, Or it is good also as the metal layer 20 which consists of two layers by sputtering the alloy which has this other metal as a main component by a well-known method. Moreover, it is good also as a multilayer film of three or more layers.

Next, a metal compound is formed of a mixture of a transparent oxide semiconductor material and a metal having an oxide generation free energy equal to or higher than that of zinc (Zn), and forms a metal compound layer 30b which is a light absorption layer having conductivity. A layer forming step is performed.
This step is performed according to the procedure of the metal compound layer forming step for forming the metal compound layer 30a.
The formation of the laminated body 1 of this embodiment is completed by the above procedure.
In the present embodiment, the metal compound layer forming step for forming the metal compound layer 30a, the metal layer forming step, and the metal compound layer forming step for forming the metal compound layer 30b are performed in this order. However, the present invention is not limited to this. However, only one of the metal compound layer forming steps may be performed.

Hereinafter, the present invention will be described in more detail based on specific examples. However, the present invention is not limited to the following embodiments.
(Test Example 1 Examination of ratio of transparent oxide semiconductor substance to metal in metal compound)
In the present test example, a metal compound layer 30a made of zinc oxide (ZnO) and copper (Cu) and a metal layer 20 made of Cu are formed on the transparent substrate 10 made of a glass substrate with ZnO in the metal compound layer 30a. The optical characteristics of the laminates 1 of Examples 1 to 4 formed by changing the Cu ratio in four stages of 8: 2, 7: 3, 6: 4, and 5: 5 were examined.

First, a target obtained by bonding a commercially available transparent oxide semiconductor material ZnO mainly composed of ZnO on a transparent substrate 10 made of a transparent glass substrate, and a target obtained by bonding Cu, which is a metal having a high free energy for generating oxide. Was set in a sputtering apparatus, and ZnO: Cu (volume ratio) was 8: 2 (Example 1), 7: 3 (Example 2), 6: 4 (Example 3), and 5: 5 (Example 4). Then, the input power was changed to form a two-source film, and the metal compound layers 30a of Examples 1 to 4 were produced.
Sputtering conditions are no heating, ultimate pressure 5.00E-4Pa, sputtering pressure 4.40E-1Pa, argon gas atmosphere, DC input power is 1.66 to 0.75 kw for ZnO target, 0.11 for Cu target The metal compound layer 30a was formed to a thickness of 40 nm with a thickness of ˜0.2 kw.

The film thickness of the formed metal compound layer 30a was 37.2 to 44.7 nm.
The specific resistance is calculated from the measured values of the film thickness and surface resistance, and the refractive index (n) and extinction coefficient of the metal compound layer are calculated from the measured values of the film thickness, transmittance, reflectance and refractive index of the substrate. (K) was calculated.
The measured value of the refractive index and the calculated value of the extinction coefficient are shown in FIGS.
2 and 3, the specific resistance is 7.32E-2 to 4.58E + 0 Ω · cm, the refractive index is 2.17 to 2.7 in the visible region (400 nm to 700 nm), and the extinction coefficient is It was 0.475 to 1.53.

  Next, on the thin film of each metal compound layer 30a of Examples 1 to 4, Cu was deposited to a thickness of 120 nm by the DC sputtering method, and the reflectance from the back side (glass side) was measured to be visible ( The average reflectance at 400 nm to 700 nm) and the difference between the maximum reflectance and the minimum reflectance were calculated. In calculating the average reflectivity and the difference between the maximum reflectivity and the minimum reflectivity, the reflectivity cancels the reflectivity of the glass surface which is the light incident surface.

The results are shown in FIGS.
As shown in FIG. 5, in Examples 2 to 4, dark black reflection was obtained with an average reflectance of 10% or less and a low reflectance with a difference between the maximum reflectance and the minimum reflectance of 5.72% or less. In Example 1, the difference between the maximum reflectance and the minimum reflectance was as large as 24.69%, and a reddish reflection was obtained.

In Example 1, the reason why the reflectance at 700 nm is high is that the thickness of the metal compound layer is thin, and the refractive index is low and the extinction coefficient is small compared to other Examples 2 to 4.
In Example 1, by calculating from the calculated refractive index and extinction coefficient, the film thickness is shifted to 50 nm, so that the maximum reflectance is 8.33%, the average reflectance is 4.08%, and the maximum and minimum. It was confirmed that the difference in reflectance was 6.57%.

As for the optical constant, it has been found that the refractive index increases and the extinction coefficient tends to increase as the Cu ratio in the metal compound layer 30a increases from 20% to 50%.
Moreover, it turned out that the value of a refractive index and an extinction coefficient becomes high, so that a measurement wavelength becomes long from 400 nm to 700 nm. This is due to the optical constant of Cu (particularly, the extinction coefficient k), and the reflectance of Cu is high in the long wavelength region around 550 nm and low in the short wavelength region. It is thought to be due to.

  In Example 1, the difference between the maximum reflectance and the minimum reflectance is as large as 24.69%, and a reddish reflection is obtained. In Example 4, the ratio of Cu in the film is increased. Therefore, the refractive index of 500 nm to 700 nm is high and the extinction coefficient is also high. Thereby, the reflectance in a long wavelength region is high, and the reflectance in a short wavelength region is low. As for the ratio of ZnO and Cu, 7: 3 of Example 2 and 6: 4 of Example 3 show good results, and the refractive index is in the range of about 2.17 to 2.54, and the extinction coefficient. Was found to be 0.66-1.20.

(Test Example 2 Examination of nitrogen gas dependency)
In this example, when the metal compound film 30a was formed by sputtering using ZnO as the transparent oxide semiconductor material, the influence of the amount of nitrogen gas introduced on the optical characteristics was examined.
In the same procedure as in Example 4 of Test Example 1, a target was prepared by mixing a transparent oxide semiconductor material ZnO and Cu, which is a metal with high oxide free energy, in a volume ratio of 5: 5.
Using this target, nitrogen gas was flowed at 0 sccm (Example 5) and 10 sccm (Example 6) with no heating, ultimate pressure 8.00E-4 Pa, sputtering pressure 1.60E-1 Pa, and input power DC 0.3 kW, respectively. ), 20 sccm (Example 7), 30 sccm (Example 8), 40 sccm (Example 9), 50 sccm (Example 10), 60 sccm (Example 11), 100 sccm (Example 12), and a film thickness of 40 nm as a guide. In addition, a metal compound layer 30a was formed.
Further, instead of nitrogen gas, oxygen gas was introduced at a flow rate of 5 sccm (Example 13) and 10 sccm (Example 14) to form a film in the same manner.

About the metal compound layer 30a of Examples 5-14, the refractive index (n) and extinction coefficient (k) of the metal compound layer 30a are determined from the film thickness, transmittance, reflectance, and refractive index of the substrate as in Test Example 1. The same calculation was performed.
The results are shown in FIGS.
As shown in FIGS. 6 and 7, in the metal compound layers 30a of Examples 5 to 14, the refractive index is in the range of 1.95 to 2.71 in the visible region (400 nm to 700 nm), and the extinction coefficient is The range was 0.90 to 1.57.
Next, on the metal compound layer 30a of Examples 5 to 14, Cu was deposited as a 120 nm metal layer 20 by a DC sputtering method to produce the laminate 1 of Examples 5 to 14. From the back surface side (glass surface side), the reflectance of the laminate 1 of Examples 5 to 14 was measured, and the average reflectance in the visible region (400 nm to 700 nm), the difference between the maximum reflectance and the minimum reflectance was calculated. .

The measurement result of the reflectance of the laminated body 1 of Examples 5 to 12 is shown in FIG. 8, and the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminated body 1 of Examples 5 to 14 are shown in FIG. .
As shown in FIG. 9, the average reflectance was 15% or less, and the difference between the maximum reflectance and the minimum reflectance was 10% or less in the range of the nitrogen flow rates of Examples 6 to 12 in the range of 10 sccm to 100 sccm. The reflectivity was 10% or less, and the difference between the maximum reflectivity and the minimum reflectivity was 5% or less when the nitrogen flow rate was 20 sccm to 100 sccm in Examples 7 to 12 and the oxygen flow rate was 10 sccm in Example 14. .

Further, it was in the range of nitrogen flow rates of 30 to 60 sccm in Examples 8 to 11 that the average reflectance was 10% or less and the difference between the maximum reflectance and the minimum reflectance was 2.5% or less. It was. As a standard for good reflectance, the average reflectance is 10% or less, and the difference between the maximum reflectance and the minimum reflectance is 2.5% or less. The reason is that reflection is sufficient when the average reflectance is 10% or less. This is because, when the difference between the maximum reflectance and the minimum reflectance is 2.5% or less, dark black without redness, yellowness, blueness, or the like is obtained.
Similarly, looking at the refractive index and the extinction coefficient, in Examples 7 to 12 and 14, the refractive index is in the range of 2.17 to 2.71 and the extinction coefficient is in the range of 0.9 to 1.57. However, in Examples 8 to 11 exhibiting dark black color with lower reflection, it was found that the refractive index was 2.25 to 2.66 and the extinction coefficient was 1.20 to 1.57.

  Even when oxygen gas is introduced at the time of sputtering, the average reflectance is reduced from the 10% level to about 4% at the oxygen flow rate of 10 sccm of Example 14 as compared to the oxygen flow rate of 5 sccm of Example 13. Since the difference between the maximum reflectance and the minimum reflectance is also reduced from about 5% to about 3%, the refractive index and extinction coefficient can be controlled by selecting the optimum amount of introduced gas, and the low reflection It turned out that the laminated body 1 which exhibits dark black can be produced.

(Test Example 3 Examples of other components of metal compounds)
In this example, indium oxide (In ₂ O ₃ ) is used instead of ZnO in Test Examples 1 and 2 as the transparent oxide semiconductor material constituting the metal compound layer 30a, and the metal having a high free energy for oxide formation is Cu. A study was conducted using Mo instead of.
A target bonded with a transparent oxide semiconductor material mainly composed of In ₂ O ₃ and a target bonded with Mo are set in a sputtering apparatus, respectively, and the two volume ratios of the transparent oxide semiconductor material: Mo are 10: 1 ( Example 15) 10: 2 (Example 16) 10: 3 (Example 17) 10: 4 (Example 18) 10: 5 (Example 19) 10:10 (Example 20) As described above, the two-source film was formed by changing the input power to produce the metal compound layers 30a of Examples 15 to 19.
Sputtering conditions were as follows: no heating, ultimate pressure 8.00E-4Pa, sputtering pressure 1.60E-1Pa, Ar atmosphere, DC input power of transparent oxide semiconductor material in the range of 0.18 kw to 0.46 kw, Mo The metal compound layer 30a was formed by two-source sputtering with a DC input power in the range of 0.1 kw to 0.45 kw and a film thickness of 40 nm as a guide.

Then, Cu was formed into a film of 120 nm by a DC sputtering method on the thin film of the metal compound layer 30a of each of Examples 15 to 19, and the reflectance from the back surface side (glass surface side) was measured. The average reflectance at ˜700 nm), the difference between the maximum reflectance and the minimum reflectance was calculated.
The measured values of the reflectance are shown in FIG. 10, and the difference between the average reflectance and the maximum reflectance and the minimum reflectance is shown in FIG.
Example 17 in which the DC input power ratio of the transparent oxide semiconductor material and Mo is 10: 3 and 10: 4 is that the average reflectance is 15% or less and the difference between the maximum reflectance and the minimum reflectance is 10% or less. , 18. In Example 17, the average reflectance is 11.56%, and the difference between the maximum reflectance and the minimum reflectance is 3.40%. In Example 18, the average reflectance is 14.02%, and the maximum reflectance. And the difference between the minimum reflectance and 3.13%.
In Examples 16 and 19 of 10: 2, 5 the average reflectivity is as high as a little less than 17%, but the difference between the maximum reflectivity and the minimum reflectivity is 3.71% and 4.16%. Had a dark black color.

(Test Example 4 Examination of constituent materials of metal compound layer)
In this example, ZnO, Cu, a metal compound layer 30a made of an alloy of _In 2 _{O 3,} by changing the ratio of ZnO and Cu and _In 2 _{O 3} was deposited, were studied suitable ratio.
A target of ZnO, which is a transparent oxide semiconductor material, and Cu, which is a metal having a high free energy for oxide formation, having a volume ratio of 5: 5 and an In ₂ O ₃ target are set in a sputtering apparatus, and a ZnO / Cu mixture is obtained. And the volume ratio of In ₂ O ₃ are 10: 1 (Example 21), 10: 2 (Example 22), 10: 3 (Example 23), 10: 4 (Example 24), 10: 5. Two-source film formation was performed by changing the ratio of input power so as to be (Example 25), and the metal compound layers 30a of Examples 21 to 25 were produced.
Sputtering conditions are as follows: No heating, ultimate pressure of 8.00E-4Pa, sputtering pressure of 1.60E-1Pa, argon (Ar) atmosphere, DC input power of ZnO / Cu mixture target in the range of 0.14kw to 0.72kw The metal compound layer 30a was formed by two-source sputtering with an In ₂ O ₃ target DC input power of 0.1 kW and a film thickness of 40 nm as a guide.

Then, Cu was formed into a film of 120 nm by a DC sputtering method on the thin film of the metal compound 30a of each of Examples 21 to 25, and the reflectance from the back surface side (glass surface side) was measured. The average reflectance at 700 nm), the difference between the maximum reflectance and the minimum reflectance was calculated.
The measured values of the reflectance are shown in FIG. 12, and the difference between the maximum reflectance and the minimum reflectance is shown in FIG.
The average reflectance is 15% or less, and the difference between the maximum reflectance and the minimum reflectance is 10% or less. The ratio of the DC input power between the ZnO / Cu mixed target and the In ₂ O ₃ target is 10: 3 to 5 Examples 23-25. In Example 23, the average reflectance is 12.92%, the difference between the maximum reflectance and the minimum reflectance is 6.17%, and in Example 24, the average reflectance is 11.79%, and the maximum reflectance and the minimum reflectance. The difference from the reflectance was 5.80%, and in Example 25, the average reflectance was 9.38%, and the difference between the maximum reflectance and the minimum reflectance was 4.64%.
In the range of this test example, as the ratio of In ₂ O ₃ increases, the difference between the average reflectivity, the maximum reflectivity, and the minimum reflectivity becomes smaller, and a laminate having good optical characteristics that more meets the purpose of the present invention. 1 was obtained.

(Test Example 5: Examination of constituent materials of metal compound layer)
In this example, instead SnO ₂ used in the _In 2 _{O 3} Test Example 4, ZnO, Cu, a metal compound layer 30a consisting of SnO ₂ alloy, formed by changing the ratio of ZnO and Cu and SnO ₂ Membranes were examined for suitable ratios.
An SnO ₂ target was set in the sputtering apparatus instead of the In ₂ O ₃ target of Test Example 4, and the volume ratio of the ZnO / Cu mixture to SnO ₂ was 10: 1 (Example 26), 10: 2 (implementation). Example 27) Two-source film formation was performed by changing the ratio of input power so as to be 10: 3 (Example 28), 10: 4 (Example 29), and 10: 5 (Example 30). ~ 30 metal compound layers 30a were prepared.
Sputtering conditions were as follows: the DC input power of the ZnO / Cu mixture target was in the range of 0.15 kW to 0.75 kw; the DC input power of the SnO ₂ target was 0.1 kW; Was deposited.

Then, Cu was formed into a film of 120 nm by a DC sputtering method on the thin film of the metal compound layer 30a of each of Examples 21 to 25, and the reflectance from the back side (glass side) was measured to be visible (400 nm The average reflectance at ˜700 nm), the difference between the maximum reflectance and the minimum reflectance was calculated.
The measured values of the reflectance are shown in FIG. 14, and the difference between the maximum reflectance and the minimum reflectance is shown in FIG.
Example 28 where the DC input power ratio of the ZnO / Cu mixture target and the SnO ₂ target was 10: 3 to 5 was that the average reflectance was 15% or less and the difference between the maximum reflectance and the minimum reflectance was 10% or less. ~ 30.

In Example 28, the average reflectance is 13.12%, and the difference between the maximum reflectance and the minimum reflectance is 6.17%. In Example 29, the average reflectance is 9.94% and the maximum reflectance is The difference from the minimum reflectance was 5.44%. In Example 30, the average reflectance was 8.69%, and the difference between the maximum reflectance and the minimum reflectance was 6.99%.
Similar to the case of using the In ₂ O ₃ target of Test Example 4, the average reflectivity decreases as the SnO ₂ ratio increases, but the bottom is generated at the ratio of Example 29 of 10: 4. The ratio of the mixture to SnO ₂ was found to be 10: 4.

(Test Example 6 Investigation of dependence on nitrogen gas when two types of transparent oxide semiconductor materials are used)
In this example, when the metal compound film 30a is formed by sputtering using two kinds of ZnO and SnO ₂ as transparent oxide semiconductor materials, the influence of the amount of nitrogen gas introduced on the optical characteristics was examined.
A target in which ZnO, which is a transparent oxide semiconductor material, Cu, which is a metal having a high free energy for oxide generation, and SnO ₂ are mixed so as to have a volume ratio of 2: 3: 1 is prepared, and the sputtering apparatus is used. I set it.
Sputtering conditions were no heating, ultimate pressure 8.00E-4 Pa, sputtering pressure 1.60E-1 Pa, DC input power 0.3 kW, Ar gas 120 sccm, nitrogen gas 0 sccm (Example 31), 20 sccm, respectively. (Example 32), 40 sccm (Example 33), 60 sccm (Example 34), 80 sccm (Example 35), 100 sccm (Example 36) were introduced, and each film was formed with a film thickness of 40 nm as a guide.
Then, Cu was formed into a film as a 120 nm metal layer 20 on the metal compound layer 30a of Examples 31 to 36 by the DC sputtering method, and the laminate 1 of Examples 31 to 36 was produced. From the back surface side (glass surface side), the reflectance of the laminated body 1 of Examples 31 to 36 was measured, and the average reflectance in the visible region (400 nm to 700 nm), the difference between the maximum reflectance and the minimum reflectance was calculated. .
The measurement result of the reflectance of the laminated body 1 of Examples 31-36 is shown in FIG. 16, and the difference between the average reflectance and the maximum reflectance and the minimum reflectance is shown in FIG.

As shown in FIG. 16, the average reflectivity was 15% or less, and the difference between the maximum reflectivity and the minimum reflectivity was 10% or less when the nitrogen flow rates of Examples 32-36 were 20 sccm to 100 sccm. . In Example 32 (nitrogen 20 sccm), the average reflectance is 13.17%, and the difference between the maximum reflectance and the minimum reflectance is 2.78%. In Example 36 (nitrogen 100 sccm), the average reflectance is 2 The difference between the maximum reflectance and the minimum reflectance was 6.76%. The average reflectance gradually decreased as the nitrogen flow rate increased, and conversely, the difference between the maximum reflectance and the minimum reflectance increased.
In Example 31 (nitrogen 0 sccm), the reflectance at a wavelength of 550 nm or higher was as high as 23% or higher. This is because the characteristics of the reflectance of Cu are greatly affected.
In addition, the reflectance decreased as the amount of nitrogen introduced increased, indicating that Cu was nitrided when the metal compound was formed by introducing nitrogen.

(Test Example 7: Examination of the amount of nitrogen introduced into the metal compound layer when the metal layer is composed of a MoNb film and an AlNd film)
In the case where the metal layer 20 in FIG. 1 has a two-layer structure of a MoNb thin film and an AlNd thin film, the influence of the nitrogen flow rate during the formation of the metal compound layer 30a on the reflectance characteristics of the laminate 1 was examined.
A target having a volume ratio of 5: 5 between ZnO, which is a transparent oxide semiconductor material, and Cu, which is a metal having high oxide generation free energy, was prepared and set in a sputtering apparatus.
Sputtering conditions were no heating, ultimate pressure 8.00E-4Pa, sputtering pressure 1.60E-1Pa, DC input power 0.3 kW, Ar gas 120 sccm, nitrogen gas 20 sccm (Example 37), 40 sccm, respectively. (Example 38), 60 sccm (Example 39), 80 sccm (Example 40), and 100 sccm (Example 41) were introduced, and a film thickness of 40 nm was formed as a guide.
Thereafter, a molybdenum alloy (MoNb) film of 25 nm was formed as the metal layer 20 on the metal compound layer 30a of Examples 37 to 41, and then an aluminum alloy (AlNd) film of 100 nm was formed, and the MoNb film and the AlNd film were formed. A metal layer 20 having a two-layer structure was formed. From the back surface side (glass surface side), the reflectance of the laminate 1 of Examples 37 to 41 was measured, and the average reflectance in the visible region (400 nm to 700 nm), the difference between the maximum reflectance and the minimum reflectance was calculated. .
The measurement result of the reflectance of the laminated body 1 of Examples 37 to 41 is shown in FIG. 18, and the difference between the average reflectance and the maximum reflectance and the minimum reflectance is shown in FIG.

As shown in FIG. 19, the average reflectance was 15% or less, and the difference between the maximum reflectance and the minimum reflectance was 10% or less when the nitrogen flow rates of Examples 39 to 41 were 60 sccm to 100 sccm. In Example 39 (nitrogen flow rate 60 sccm), the average reflectance was 13.71%, and the difference between the maximum reflectance and the minimum reflectance was 5.71%. In Example 41 (nitrogen flow rate 100 sccm), the average reflectance was 7.46%, and the difference between the maximum reflectance and the minimum reflectance was 2.61%.
In this example, unlike the result of Test Example 5, the average reflectance, the maximum reflectance, the minimum reflectance, the maximum reflectance and the minimum reflectance are increased as the nitrogen flow rate during the formation of the metal compound layer 30a increases from 20 sccm to 100 sccm. All of the difference values were lower, indicating better optical properties. From this result, it was found that Cu scattered from the target was nitrided by introducing nitrogen during sputtering.
In addition, in the range of 20 sccm to 100 sccm, the reflectivity continues to decrease as the nitrogen flow rate increases, and the average reflectivity, maximum reflectivity, minimum reflectivity, Since none of the difference values between the reflectance and the minimum reflectance reached the bottom, it was found that a laminated film having a better low reflectance can be obtained by further increasing the amount of nitrogen introduced to 100 sccm or more.

(Test Example 8 Examination of metal compound film thickness when the metal layer is an AlNd film or an APC film)
When the metal layer 20 of FIG. 1 is an Al alloy (AlNd) film or an Ag alloy (APC: Ag—Pd—Cu alloy) film, the film thickness of the metal compound layer 30 a is related to the reflectance characteristics of the laminate 1. The effect was examined.
A target having a volume ratio of 5: 5 between ZnO, which is a transparent oxide semiconductor material, and Cu, which is a metal having high oxide generation free energy, was prepared and set in a sputtering apparatus.
Sputtering conditions are no heating, ultimate pressure 8.00E-4 Pa, sputtering pressure 1.60E-1 Pa, DC input power 0.3 kW, Ar gas 120 sccm and nitrogen gas 60 sccm introduced in an atmosphere of ZnO which is a metal compound A Cu film was formed to have a film thickness of 40 nm, 50 nm, and 60 nm to obtain a metal compound layer 30a.

Thereafter, an aluminum alloy (AlNd) 100 nm or an Ag alloy (APC) 100 nm is formed as the metal layer 20 on the metal compound layer 30 a having a film thickness of 40 nm, 50 nm, and 60 nm, respectively. Filmed.
When the metal compound layer 30a has a film thickness of 40 nm, 50 nm, and 60 nm and the metal layer 20 is AlNd, it is referred to as Examples 42 to 44, respectively, and the metal compound layer 30a has a film thickness of 40 nm, 50 nm, and 60 nm. The case where the layer 20 was APC was made into Examples 45-47, respectively.
From the back surface side (glass surface side), the reflectance of the laminated body 1 of Examples 42 to 47 was measured, and the average reflectance in the visible region (400 nm to 700 nm), the difference between the maximum reflectance and the minimum reflectance was calculated. .
The measurement result of the reflectance of the laminated body 1 of Examples 42 to 47 is shown in FIG. 20, and the difference between the average reflectance and the maximum reflectance and the minimum reflectance is shown in FIG.

  In Example 42 in which AlNd was formed on the metal compound layer 30a having a thickness of 40 nm, the difference between the maximum reflectance and the minimum reflectance was 10.68%, but in Examples 43 to 47, the average reflectance was 6.22% to 11.0%, and the difference between the maximum reflectance and the minimum reflectance is in the range of 4.36% to 6.71%. The laminated body 1 was able to be obtained.

(Test Example 9 Etchability Evaluation)
In this example, the etching property of the laminate 1 manufactured under the conditions of Example 6 (nitrogen flow rate 10 sccm), Example 11 (nitrogen flow rate 60 sccm), and Example 12 (nitrogen flow rate 100 sccm) of Test Example 2 was evaluated. .
Sputtering was performed on a substrate 10 made of a glass substrate under the same conditions as in Examples 11 and 12 of Test Example 2 at a nitrogen flow rate of 60 sccm and 100 sccm from a target in which ZnO and Cu were mixed at a volume ratio of 5: 5. A metal compound layer 30a having a film thickness of 40 nm was formed, and a metal layer 20 made of Cu having a film thickness of 120 nm was formed on the metal compound layer 30a by sputtering to obtain the laminates 1 of Examples 48 and 49, respectively. .

Further, under the same conditions as in Example 6 of Test Example 2, sputtering was performed on a substrate 10 made of a glass substrate at a nitrogen flow rate of 10 sccm from a target in which ZnO and Cu were mixed at a volume ratio of 5: 5. A metal compound layer 30a having a thickness of 40 nm was formed, and a metal layer 20 made of Cu having a thickness of 120 nm was formed on the metal compound layer 30a by sputtering, whereby the laminate 1 of Example 50 was obtained.
Under the same conditions as in Example 11 of Test Example 2, sputtering was performed on a substrate 10 made of a PET film from a target in which ZnO and Cu were mixed at a volume ratio of 5: 5 at a nitrogen flow rate of 60 sccm, and the film thickness was 40 nm. A metal compound layer 30a was formed, and a metal layer 20 made of Cu having a thickness of 120 nm was formed on the metal compound layer 30a by sputtering, whereby the laminate 1 of Example 51 was obtained.

  Under the same conditions as in Example 6 of Test Example 2, sputtering was performed on a substrate 10 made of a PET film using a target in which ZnO and Cu were mixed at a volume ratio of 5: 5 at a nitrogen flow rate of 60 sccm. A metal compound layer 30a with a thickness of 40 nm is formed, a metal layer 20 made of Cu with a thickness of 120 nm is formed on the metal compound layer 30a by sputtering, and a volume ratio of ZnO and Cu is 5: 5 at a nitrogen flow rate of 60 sccm. Sputtering was performed using the target mixed in step 1 to form a metal compound layer 30b having a thickness of 40 nm, whereby the laminate 1 of Example 52 was obtained.

About the laminated body of Examples 48-52, two types, nitric acid and hydrogen peroxide type (Ech-1, made by Geomatic Co., Ltd.) and phosphoric acid, nitric acid and acetic acid type (Ech-2, made by Geomatic Co., Ltd.) Etching was performed using an etchant.
In the etching procedure, each of the laminates 1 of Examples 48 to 52 was cut into 50 mm × 50 mm, immersed in each etchant, and controlled so that the liquid temperature was constant, and the etching end time (end point) was set. confirmed.

The etching end points of Examples 48 to 50 using a glass substrate are nitric acid / hydrogen peroxide (Ech-1) etchants, both of which are 20 seconds, the same time, and phosphoric acid / nitric acid / acetic acid (Ech). The etchant of -2) was 45 to 50 seconds and took more than twice as long as Ech-1.
The etching end points of Examples 51 and 52 using the film substrate are 17 to 18 seconds for the nitric acid / hydrogen peroxide (Ech-1) etchant, and the phosphoric acid / nitric acid / acetic acid (Ech-2) etchant. 38 to 44 seconds, which is about 10% of the results of Examples 48 to 50 using the glass substrate, but was a little faster.

(Test Example 10: Test pattern etching evaluation)
Using the laminate 1 of Examples 48 to 52 produced in the same manner as in Test Example 9, using test patterns of 20 μm, 10 μm, and 4 μm on the plate, nitric acid / hydrogen peroxide (Ech-1) etchant and phosphorus Wet etching was performed using an acid / nitric acid / acetic acid system (Ech-2) to confirm the pattern dimensions of each sample.
The results are shown in Table 1.

In Table 1, the pattern width is the measured value of the pattern width obtained after etching, and the receding width is the resist pattern by dividing the average value of the difference between the resist width at each resist width and the measured value of the pattern width by 2. It is the value which calculated the average value of the one-side dimension of the retreat with respect to.
As shown in Table 1, in the nitric acid / hydrogen peroxide-based (Ech-1) etchant, the one-side dimension with respect to the resist pattern averaged about 0.5 to 0.6 μm (overetch). However, a pattern based on 20 μm, 10 μm, and 4 μm could be formed. It was a good pattern when observed from either the front or back side.
In the phosphoric acid / nitric acid / acetic acid (Ech-2) etchant, although the 20 μm pattern was confirmed, the 10 μm and 4 μm patterns could not be confirmed, and the pattern of the metal layer 20 was overhanged. Sufficient results were not obtained.
However, it was found that reliable pattern formation was possible with any etchant by adjusting the etchant concentration and blending ratio.

(Test Example 11 Test Pattern Etching Evaluation)
In this example, the etching property of the laminate 1 manufactured under the condition of Example 30 of Test Example 5 (the volume ratio of the ZnO / Cu mixture and SnO ₂ is 10: 5) was evaluated.
A metal having a thickness of 40 nm was formed by sputtering on the substrate 10 made of a glass substrate under the same conditions as in Example 30 of Test Example 5 so that the volume ratio of the ZnO / Cu mixture and SnO ₂ was 10: 5. A compound layer 30a is formed, a metal layer 20 made of Cu having a thickness of 120 nm is formed on the metal compound layer 30a by sputtering, and the volume ratio of the ZnO / Cu mixture and SnO ₂ is 10: 5. Sputtering was performed to form a metal compound layer 30b having a thickness of 40 nm to obtain a laminate 1 of Example 53.

Using the laminate 1 of Example 53, a nitric acid / hydrogen peroxide (Ech-1) etchant and an iron chloride etchant (Ech-3, manufactured by Geomatic Co., Ltd.) with a test pattern of 20 μm, 10 μm, and 4 μm were used. Etching was performed using a plate to confirm the pattern dimensions of the sample.
The results are shown in Table 2.

  From the results in Table 2, the nitric acid / hydrogen peroxide-based (Ech-1) etchant has an average one-sided recession (overetch) with respect to the resist pattern (overetch), and the iron chloride etchant (Ech) 3), the pattern was backed by about 0.5 μm (overetch), and a pattern based on 20 μm, 10 μm, and 4 μm could be formed. However, in the etchant of iron chloride (Ech-3), since the etching rate of the metal compound layers 30a and 30b was fast, even when viewed from either the front or back surface, slight reflection by Cu was confirmed at the pattern edge portion.

(Test Example 12 Example in which the metal compound layer is composed of a mixture of two kinds of metals)
On the substrate 10, a metal compound layer 30 a composed of two kinds of metals, Cu and Ni, and ZnO was formed, and then Cu was used as the metal layer 20. First, two alloy targets of Cu and Ni (1: 1) and a ZnO target are set in the apparatus, and each target is set to have a ratio of Cu: Ni: ZnO = 1: 1: 1-5. Were adjusted to form five types of metal compound layers 30a having a thickness of approximately 55 nm by two-source sputtering.
Sputtering conditions are no heating, ultimate pressure 5.00E-4Pa, sputtering pressure 4.3E-1Pa, and argon gas atmosphere. DC input power is 1.66 to 0.35 kW for ZnO target and 0.2 kW for Cu target. Thus, the metal compound layer 30a was formed aiming at a film thickness of 55 nm. Next, a metal layer 20 made of Cu having a film thickness of 120 nm was formed on the metal compound layer 30a by sputtering using another Cu target to obtain laminates of Examples 54 to 58.

Furthermore, in the ratio of Cu: Ni: ZnO = 1: 1: 1, oxygen 2 sccm and 4 sccm were introduced at the time of film formation to obtain the laminates of Examples 59-60.
From the metal compound layer 30a side (glass surface side), the reflectances of the laminates of Examples 54 to 60 were measured, and the average reflectance in the visible range (400 nm to 700 nm), the difference between the maximum reflectance and the minimum reflectance was determined. Calculated. 22 and 23 show the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminates of Examples 54 to 60, and FIG. 24 shows the measurement results of the reflectance.
When oxygen was not introduced during film formation, the average reflectance was 15% or less, and the difference between the maximum reflectance and the minimum reflectance was 10% or less. As shown in FIG. 23, the ratio of Cu: Ni: ZnO was Example 1: 55 to 57, which was 1: 1 to 2-4.
In the case where oxygen was not introduced at the time of film formation, the reflectivity did not reach the expected reflectivity level of 15% or less in Example 54 having a ratio of 1: 1: 1 and Example 58 having a 1: 1: 5 ratio. In Example 58 where the oxide ratio was as high as 1: 1: 5, it is considered that the reflectance was increased because the absorption of the metal compound layer was reduced.
On the other hand, when the ratio was 1: 1: 1, in Examples 59 and 60 of FIGS. 23 and 24, the reaction gas such as oxygen gas O ₂ = ₂ sccm and 4 sccm was introduced and adjusted during film formation. In Example 59, the average reflectance was 15.75%, and the difference between the maximum reflectance and the minimum reflectance was 5.65%. In Example 60, the average reflectance was 14.78%, and the difference between the maximum reflectance and the minimum reflectance was It was found that the reflectance was reduced to 6.12% and good reflectance was obtained.

(Test Example 13) The metal compound layer is composed of one type of metal (Mo) and two types of dielectrics.
As a transparent oxide semiconductor material constituting the metal compound layer 30a, the ratio of ZnO, aluminum oxide (Al ₂ O ₃ ) and Mo is (5: 1: 3), (4.5: 1.5: 3), ( An oxide mixed target of 4: 2: 3) was prepared.
An oxide mixed target was set in the apparatus, and sputtering conditions were as follows: no heating, ultimate pressure of 8.00E-4Pa, sputtering pressure of 1.60E-1Pa, Ar gas of 120sccm, input power of 0.3kW, and metal oxide After the layer 30a was formed, an AlNd alloy was stacked to 120 nm to form the metal layer 20, and the stacked bodies of Examples 61 to 63 were obtained.

From the metal compound layer 30a side (glass surface side), the reflectance of the laminates of Examples 61 to 63 was measured, and the average reflectance in the visible region (400 nm to 700 nm), the difference between the maximum reflectance and the minimum reflectance was determined. Calculated. The average reflectance of the laminates of Examples 61 to 63 and the difference between the maximum reflectance and the minimum reflectance are shown in FIG. 25, and the measurement results of the reflectance are shown in FIG.
As shown in FIGS. 25 and 26, the average reflectance and the difference between the maximum reflectance and the minimum reflectance in Examples 61 to 63 are all 10% or less, and a good dark black film as viewed from the viewing side is formed. I was able to get it. A large difference due to the ratio between ZnO and Al ₂ O ₃ was not observed.

Further, 50 nm of Cu and Al were respectively formed on the metal compound layer 30a having the ratio of ZnO, Al ₂ O ₃ and Mo of Example 62 of 4.5: 1.5: 3, and the metal layer 20 was formed in two layers. A laminated structure of Examples 64 and 65 was obtained with a layer structure.
In Examples 64 and 65, the average reflectivity and the difference between the maximum reflectivity and the minimum reflectivity were all 10% or less. However, at a film thickness of 50 nm, in many regions in the visible range of 400 to 700 nm, Cu was more than Cu. It was also found that the reflectance was lower when Al was deposited. This is presumably because the peak of the minimum reflectance serving as the bottom of the reflectance is shifted due to the influence of the refractive index and extinction coefficient of Cu and Al. When forming the Cu film, the difference between the average reflectance and the maximum reflectance and the minimum reflectance in Example 64 may be reduced by reducing the film thickness of the metal compound layer 30a to 35 nm to 40 nm. .

Further, the film thickness of the metal compound layer 30a in which the ratio of ZnO, Al ₂ O ₃ and Mo in Example 62 is 4.5: 1.5: 3 is varied between 40 nm and 60 nm in increments of 5 nm. Then, a metal layer 20 made of an AlNd alloy was formed to obtain the laminates of Examples 66 to 70.
From the metal compound layer 30a side (glass surface side), the reflectances of the laminates of Examples 66 to 70 were measured, and the average reflectance in the visible region (400 nm to 700 nm), the difference between the maximum reflectance and the minimum reflectance was determined. Calculated. FIG. 29 shows the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminates of Examples 66 to 70, and FIG. 30 shows the measurement results of the reflectance.
As shown in FIG. 29, in Examples 66 to 69, the average reflectance was 15% or less, and the difference between the maximum reflectance and the minimum reflectance was 10% or less. In Example 70, the difference between the maximum reflectance and the minimum reflectance was 12.78%, and the average reflectance was 7.50%, which is 15% or less. In FIG. 29, as a matter of course, the film thickness dependency is clearly shown. As described above, this can be easily expected to be applied when the metal layer 20 is made of Cu.

(Test Example 14 Example of Metal Compound Layer (ZnO: Cu = 1: 1) and One Type of Metal Oxide)
As a transparent oxide semiconductor material constituting the metal compound layer 30a, a target of ZnO and Cu in a ratio of 1: 1 and an Al ₂ O ₃ target are set in the apparatus to form the metal compound layer 30a (ZnO: Cu = 1: 1) and one kind of metal oxide (Al ₂ O ₃ ) so that the ratio of each sputtering power supply is (ZnO—Cu) :( Al ₂ O ₃ ) = 10: 3.5. By adjusting the output, three types of metal compound layers 30a were formed aiming at film thicknesses of 35 nm, 50 nm, and 65 nm. Then, 120 nm of Cu was laminated as the metal layer 20 to obtain laminates of Examples 71 to 73.

From the metal compound layer 30a side (glass surface side), the reflectances of the laminates of Examples 71 to 73 were measured, and the average reflectance in the visible region (400 nm to 700 nm), the difference between the maximum reflectance and the minimum reflectance was determined. Calculated. FIG. 31 shows the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminates of Examples 71 to 73, and FIG. 32 shows the measurement results of the reflectance.
In Examples 71 and 72 in which the film thickness of the metal compound layer 30a was 35 and 50 nm, the average reflectance was 15% or less, and the difference between the maximum reflectance and the minimum reflectance was 10% or less. In Example 73 where the film thickness of the metal compound layer 30a was 65 nm, the difference between the maximum reflectance and the minimum reflectance was 2.41%, which is 10% or less, and the average reflectance was 16.25%.
Even when the metal compound layer 30a has a film thickness of 35 nm, 50 nm, or 65 nm, a reflectance with good flatness could be obtained. In Example 73 in which the film thickness of the metal compound layer 30a is 65 nm, the reflectivity as a whole in the visible range is high, but since the difference between the maximum reflectivity and the minimum reflectivity is small, it is darkened. It was good.

  In a conventional laminated body in which a layer of a transparent oxide semiconductor material and a metal layer are simply combined, the reflectance is reduced and the interference color due to the bottom tends to become clear due to the relationship between the refractive index and the extinction coefficient. On the other hand, it is possible to obtain a laminated film exhibiting a more preferable dark black color by combining a metal compound layer made of a mixture with a metal having an oxide generation free energy equivalent to or higher than that of the zinc oxide of the present application and a metal layer. It was found from the above examples that

DESCRIPTION OF SYMBOLS 1 Laminated body 20 Metal layer 30a, 30b Metal oxide layer

Metals having an oxide generation free energy equivalent to or higher than that of zinc (Zn) include copper (Cu), nickel (Ni), molybdenum (Mo), cobalt (Co), lead (Pb), etc., and the horizontal axis represents temperature. the vertical axis in Ellingham diagram of a generic oxides with a standard free energy of oxide formation, can be selected metal located above the Zn equal to or Zn.
The metal mixed in the metal compound layers 30a and 30b is a metal having an oxide generation free energy equivalent to or higher than that of zinc (Zn). When a thin film is formed by mixing with a semiconductor material, it reacts too much with oxygen and acts only as a mere additive of the transparent oxide semiconductor material to obtain a thin film having a desired optical constant with a large absorption. Because it becomes difficult.

<The manufacturing method of the laminated body 1>
In the laminate 1 of this embodiment, at least one layer of a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm or an alloy containing the metal as a main component is formed on a transparent substrate 10. At least one of the metal layer forming step for forming the metal layer 20 having a resistance of 10 μΩ · cm or less, and before and after the metal layer forming step, is equal to or more than the transparent oxide semiconductor material and zinc (Zn). A metal compound layer forming step for forming a metal compound layer 30a, 30b, which is a light absorption layer having conductivity, by forming a film with a mixture of at least one kind of metal having free oxide generation energy Manufactured by.
Hereinafter, the manufacturing method of the laminated body 1 of this embodiment is demonstrated.
First, a metal compound that forms a metal compound layer 30a, which is a light absorption layer having conductivity, made of a mixture of a transparent oxide semiconductor material and a metal having an oxide generation free energy equal to or higher than that of zinc (Zn) A layer forming step is performed.
In this step, a target bonded with a transparent oxide semiconductor material, a target bonded with a metal having an oxide generation free energy equal to or higher than that of zinc (Zn), and a transparent substrate 10 are set in a sputtering apparatus and transparent. Transparent oxide semiconductor material so that the volume ratio in the film of the oxide semiconductor material and a metal having oxide generation free energy equal to or higher than zinc (Zn) is in the range of 8: 2 to 5: 5 The metal compound layer 30a is formed into a two-source film by sputtering by adjusting the input power of the target bonded to the target and the target bonded to the metal having a free energy for generating an oxide equal to or higher than that of zinc (Zn).

At this time, a single transparent oxide semiconductor material and a metal having an oxide generation free energy equal to or higher than that of zinc (Zn) are previously mixed at a volume ratio of 8: 2 to 5: 5. Sputtering may be performed using a target, and a transparent oxide semiconductor material and a metal having an oxide generation free energy equal to or higher than that of zinc (Zn) are mixed at a volume ratio of 8: 2 to 5: 5. Alternatively, a two-source film formation may be performed using another target and a metal target having an oxide generation free energy equal to or higher than that of another transparent oxide semiconductor material and / or zinc (Zn).

Next, a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm or a metal layer having a specific resistance of 10 μΩ · cm or less is formed by forming at least one layer of a metal having a specific resistance of 10 μΩ · cm or an alloy containing the metal as a main component. A layer forming step is performed.
In this step, a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm or an alloy containing the metal as a main component is formed by sputtering using a known method so as to have a film thickness of about 120 nm. Further, after sputtering a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm or an alloy containing the metal as a main component by a known method, a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm It is good also as the metal layer 20 which consists of two layers by sputtering another metal or the alloy which has this other metal as a main component by a well-known method. Moreover, it is good also as a multilayer film of three or more layers.

(Test Example 2 Examination of nitrogen gas dependency)
In this example, when the metal compound layer 30a was formed by sputtering using ZnO as the transparent oxide semiconductor material, the influence of the amount of nitrogen gas introduced on the optical characteristics was examined.
In the same procedure as in Example 4 of Test Example 1, a target was prepared by mixing a transparent oxide semiconductor material ZnO and Cu, which is a metal with high oxide free energy, in a volume ratio of 5: 5.
Using this target, nitrogen gas was flowed at 0 sccm (Example 5) and 10 sccm (Example 6) with no heating, ultimate pressure 8.00E-4 Pa, sputtering pressure 1.60E-1 Pa, and input power DC 0.3 kW, respectively. ), 20 sccm (Example 7), 30 sccm (Example 8), 40 sccm (Example 9), 50 sccm (Example 10), 60 sccm (Example 11), 100 sccm (Example 12), and a film thickness of 40 nm as a guide. In addition, a metal compound layer 30a was formed.
Further, instead of nitrogen gas, oxygen gas was introduced at a flow rate of 5 sccm (Example 13) and 10 sccm (Example 14) to form a film in the same manner.

Then, Cu was formed into a film of 120 nm by a DC sputtering method on the thin film of the metal compound layer 30a of each of Examples 21 to 25, and the reflectance from the back side (glass side) was measured to be visible (400 nm The average reflectance at ˜700 nm), the difference between the maximum reflectance and the minimum reflectance was calculated.
The measured values of the reflectance are shown in FIG. 12, and the difference between the maximum reflectance and the minimum reflectance is shown in FIG.
The average reflectance was 15% or less, and the difference between the maximum reflectance and the minimum reflectance was 10% or less. The ratio of DC input power between the ZnO / Cu mixed target and the In ₂ O ₃ target was 10: 3 to 5 Examples 23-25. In Example 23, the average reflectance is 12.92%, the difference between the maximum reflectance and the minimum reflectance is 6.17%, and in Example 24, the average reflectance is 11.79%, and the maximum reflectance and the minimum reflectance. The difference from the reflectance was 5.80%, and in Example 25, the average reflectance was 9.38%, and the difference between the maximum reflectance and the minimum reflectance was 4.64%.
In the range of this test example, as the ratio of In ₂ O ₃ increases, the difference between the average reflectance, the maximum reflectance, and the minimum reflectance becomes smaller, and a laminate having good optical characteristics that more meets the purpose of the present invention. 1 was obtained.

(Test Example 6 Investigation of dependence on nitrogen gas when two types of transparent oxide semiconductor materials are used)
In this example, as a transparent oxide semiconductor material, in the case of forming a metal compound layer 30a by sputtering using two ZnO and SnO _2, a nitrogen gas introduction rate was studied influence on the optical properties.
A target in which ZnO, which is a transparent oxide semiconductor material, Cu, which is a metal having a high free energy for oxide generation, and SnO ₂ are mixed so as to have a volume ratio of 2: 3: 1 is prepared, and the sputtering apparatus is used. I set it.
Sputtering conditions were no heating, ultimate pressure 8.00E-4 Pa, sputtering pressure 1.60E-1 Pa, DC input power 0.3 kW, Ar gas 120 sccm, nitrogen gas 0 sccm (Example 31), 20 sccm, respectively. (Example 32), 40 sccm (Example 33), 60 sccm (Example 34), 80 sccm (Example 35), 100 sccm (Example 36) were introduced, and each film was formed with a film thickness of 40 nm as a guide.
Then, Cu was formed into a film as a 120 nm metal layer 20 on the metal compound layer 30a of Examples 31 to 36 by the DC sputtering method, and the laminate 1 of Examples 31 to 36 was produced. From the back surface side (glass surface side), the reflectance of the laminated body 1 of Examples 31 to 36 was measured, and the average reflectance in the visible region (400 nm to 700 nm), the difference between the maximum reflectance and the minimum reflectance was calculated. .
The measurement result of the reflectance of the laminated body 1 of Examples 31-36 is shown in FIG. 16, and the difference between the average reflectance and the maximum reflectance and the minimum reflectance is shown in FIG.

(Test Example 13) The metal compound layer is composed of one type of metal (Mo) and two types of dielectrics.
As a transparent oxide semiconductor material constituting the metal compound layer 30a, the ratio of ZnO, aluminum oxide (Al ₂ O ₃ ) and Mo is (5: 1: 3), (4.5: 1.5: 3), ( An oxide mixed target of 4: 2: 3) was prepared.
Set the oxide mixture target in the apparatus, the sputtering conditions, without heating, the ultimate pressure 8.00E-4Pa, sputtering pressure 1.60E-1Pa, at input power 0.3kW at Ar gas 120 sccm, metallic compounds After the physical layer 30a was formed, an AlNd alloy was laminated to 120 nm to form the metal layer 20, and the laminated bodies of Examples 61 to 63 were obtained.

1 stack 20 metal layers 30a, 30b Metal compound layer

Claims (11)

A laminate comprising a transparent substrate, a metal layer formed on the substrate, and a metal compound layer formed on at least one surface of the metal layer so as to be in contact with the surface,
The metal layer comprises a metal layer having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm or a metal layer having a specific resistance of 10 μΩ · cm or less, comprising at least one layer of an alloy mainly composed of the metal.
The said metal compound layer consists of a mixture of a transparent oxide semiconductor substance and at least 1 or more types of metal which has an oxide formation free energy equivalent to or more than zinc (Zn).   The metal layer is formed by laminating the at least one alloy layer and a dissimilar metal layer made of a metal different from the metal that is a main component of the alloy layer. Item 2. The laminate according to Item 1.   The metal layer includes a single layer made of copper (Cu), aluminum (Al), silver (Ag), or an alloy of these metals, a molybdenum (Mo) layer, a molybdenum alloy layer, an aluminum (Al) layer, aluminum. The laminate according to claim 2, wherein two or three layers selected from the group consisting of alloy layers are laminated.   The metal compound layer has a refractive index (n) in the visible region (400 to 700 nm) of 2.0 to 2.8 and an extinction coefficient (k) of 0.6 to 1.6. Item 4. The laminate according to any one of Items 1 to 3. The metal compound layer includes indium oxide (In ₂ O ₃ ), zinc oxide (ZnO) or tin oxide (SnO ₂ ), or indium oxide (In ₂ O ₃ ), zinc oxide (ZnO) or tin oxide (SnO _2). ) As a main component, and a layer composed of a mixture of one or two kinds of transparent oxide semiconductor materials containing additives and a metal having an oxide generation free energy equal to or higher than that of zinc (Zn). The laminate according to any one of claims 1 to 4.   The metals having the free energy of oxide generation equal to or higher than that of zinc (Zn) are zinc (Zn), copper (Cu), nickel (Ni), molybdenum (Mo), cobalt (Co), lead (Pb), molybdenum. The laminate according to claim 5, wherein the laminate is one or more kinds of metals selected from a group including an alloy.   The metal compound layer is formed by mixing the transparent oxide semiconductor material and a metal having an oxide generation free energy equal to or higher than zinc (Zn) at a volume ratio of 8: 2 to 5: 5. The laminate according to claim 6. The metal compound layer contains one or more of the group consisting of oxygen (O), nitrogen (N), and carbon (C),
The layered product according to any one of claims 1 to 7, wherein the thickness of the metal compound layer is in a range of 30 nm to 60 nm.   In the visible region (400 to 700 nm), the reflectance with respect to light incident from the metal compound layer side of the laminate is an average of 1.0% to 15%, and the difference between the maximum reflectance and the minimum reflectance is 10%. It is the following and the laminated body of any one of Claims 1 thru | or 8 which shows a dark color visually. Comprising the laminate according to any one of claims 1 to 9,
The metal layer and a metal compound layer formed on at least one surface of the metal layer so as to be in contact with the surface are formed on at least a part of the substrate or patterned. An electronic device characterized by A metal layer having a specific resistance of 10 μΩ · cm or less is formed on a transparent substrate by depositing at least one layer of a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm or an alloy containing the metal as a main component. Forming a metal layer,
Before and after the metal layer forming step, at least one of the transparent oxide semiconductor material and a mixture of at least one kind of metal having free energy of oxide generation equal to or higher than that of zinc (Zn) is formed. And a metal compound layer forming step of forming a metal compound layer which is a light absorption layer having conductivity.

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