KR101681878B1 - Laminate, method for manufacturing same, and electronic device - Google Patents

Abstract

Disclosed is a laminate having reduced shine (reflectance) due to metallic specific luster, a method for producing the same, and an electronic apparatus.
In order to solve the above problems, the laminate of the present invention comprises a transparent substrate, a metal layer (20) formed on the substrate, and metal compound layers (30a, 30b) formed on at least one side of the metal layer ), Wherein the metal layer (20) has 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 resistivity of 10 μΩ · cm And the metal compound layers 30a and 30b are formed of a transparent oxide semiconductor material and a mixture of at least one kind of metal having an oxide formation free energy equal to or higher than that of zinc (Zn).

Description

(Laminate, method for manufacturing same, and electronic device)

The present invention relates to a laminate comprising a metal and a conductive metal compound, which can be used for a metal electrode for electronic equipment and optical equipment, a method for producing the same, and an electronic apparatus.

2. Description of the Related Art In recent years, particularly in an electrode (including an auxiliary electrode for increasing conductivity) used in various electronic devices using liquid crystal, organic EL, or the like, a touch sensor, which is an input / . Among the detecting electrodes, the wiring electrodes, and the connecting electrodes included in the touch sensor (panel), in particular, in the case of the detecting electrode, since the resistive component is increased when the touch sensor is increased in size, a lower resistance electrode is required.

Conventionally, the visibility of display has been secured by using a conductive metal oxide having high transparency, such as an oxide semiconductor containing In, Zn, Sn, Ti or the like as a main component. However, the conductive metal oxide having high transparency has a limitation in lowering the resistance value, and it is difficult to achieve a low resistance at a recently required level. As a substitute material, there is a demand for commercialization of a low resistance metal which can ensure visibility by fine patterning.

In the case of an electronic apparatus in which a substrate having electrodes on the front surface of a display element such as a touch panel is disposed, it is necessary to prevent visibility of the display. Therefore, electrodes are required to be shielded or scattered, stray light, As little as possible is required.

However, it is necessary to reduce the reflectance of a conventional electrode made of a conductive metal oxide by merely replacing the electrode with a metal because of the high reflectivity of the metal. It is also important to make the conductor as low as possible and electrically connectable.

Molybdenum (Mo), chromium (Cr), titanium (Ti), tantalum (Ta), tungsten (W), and alloys thereof are examples of metals with low reflectance. On the other hand, silver (Ag), aluminum (Al), copper (Cu), and alloys thereof have low resistance values but 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 value by using the characteristics of these metals has been proposed. However, there is a limit in reducing the reflectance by metal lamination.

Even if the reflectance can be reduced to some extent by the lamination of metals, since the etch rates of the respective metals are different from each other, it is difficult to finely process each layer in a wet etching step in particular. Further, if the wet etching process is adjusted so as to be satisfactorily performed, it is difficult to sufficiently reduce the reflectance.

As a method for reducing the reflectance, there is a method of forming a dielectric, a metal oxide, a metal nitride, a metal oxynitride and a metal carbide layer on a metal layer to form a two- or three-layer structure, or a method of arranging a metal reflection film of low reflectance on a metal layer A method of forming a dielectric material, a metal oxide, a metal nitride, a metal oxynitride, and a metal carbide layer has been proposed (for example, Patent Documents 1 to 7).

That is, Patent Document 1 discloses a laminate in which a blackening layer composed of copper nitride and oxygen is formed on a substrate as an electromagnetic wave shielding film function film for a plasma display, and the visibility of the display disposed below the touch panel is lowered A transparent conductive film which is free from the above-mentioned problems.

Patent document 2 discloses a film-type touch panel sensor in which reflection of a wiring is suppressed by forming a black copper oxide film on the viewer side of a stripe or mesh-shaped copper wiring provided on a film.

Patent Document 3 discloses a touch panel sensor capable of performing high-precision three-etching and having low resistance by forming an absorbing layer serving as an adhesion layer made of an inorganic oxide material formed on a sensor electrode and a sensor electrode made of a metal material on an insulating substrate have.

Patent Document 4 discloses an absorbing layer which is a blackening layer composed of at least one selected from the group consisting of a dielectric material, a metal, an alloy of metal, an oxide of metal, a nitride of metal, an oxynitride of metal and a carbide of metal, It is possible to improve the visibility of the conductive layer and the reflection characteristic against external light by laminating a conductive layer containing at least one selected from the group consisting of Mo, Ti, Cr, Al, Cu, Fe, Co, V, Lt; / RTI >

Patent Document 5 discloses that a blackening 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 blackening layer, a metal layer, a substrate, a blackening layer, It is disclosed that the visibility reduction of the display due to the bright metallic luminescent light is suppressed by constituting the blackening layer in the order of copper nitride and that the use of a Ni-Zn film for the metal layer and a Cu film for the conductive layer is disclosed in Patent Document 7 have.

As described above, Patent Documents 1 to 7 disclose 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 substance, and the like as a material for forming an absorbing layer.

According to the methods such as Patent Documents 1 to 7, the reflection by the metal can be absorbed by the blackening layer or the absorbing layer, and the reflectance can be further reduced by repeatedly laminating a plurality of layers.

Japanese Patent Application Laid-Open No. 2013-169712 Japanese Patent Application Laid-Open No. 2013-206315 Japanese Patent Application Laid-Open No. 2013-149196 Japanese Patent Laid-Open Publication No. 2013-540331 Japanese Patent Application Laid-Open No. 2008-311565 Japanese Patent Application Laid-Open No. 2013-129183 Japanese Patent Application Laid-Open No. 2007-308761

However, in the materials used in the absorbent layer or the blackening layer of Patent Documents 1 to 7, since the refractive index (n) in the visible region is about 1.4 to 2.5 and the extinction coefficient (k) is 0.01 to 0.25, It is a transparent thin film or layer.

Therefore, even if the absorbing layers or the blackening layers of Patent Documents 1 to 7 are laminated on the surface of the metal layer for the purpose of reducing the reflectance in the visible region, the maximum and minimum reflectance in the visible region are generated due to the interference of light, , The reflectance reduction effect as expected can not be obtained.

In Patent Documents 1 to 7, since the respective layers are repeatedly laminated, the difference in etching rate between the respective layers becomes large, so that there is a limitation on the selected material.

Since the absorbing layer or the blackening layer of Patent Documents 1 to 7 is a thin film of a metal compound, it is impossible to collectively etch the metal layer in the patterning process, so that an etchant different from the metal layer is required, Rate matching is not achieved, and either of the films in the laminated structure is subjected to overetching or underetching, so that formation of a fine pattern can not be expected.

When a metal compound other than a transparent conductive film which is a transparent oxide semiconductor material is used as the absorbing layer or the blackening layer, depending on the presence or the value of conductivity of the absorbing layer or the blackening layer, it is necessary to increase the number of steps for connection to other connecting electrodes, And there is a limitation in the case of using it as an electrode.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a laminate with reduced glare (reflectivity) caused by a specific metallic luster, a method of manufacturing the same, and an electronic apparatus.

Another object of the present invention is to provide a method of manufacturing a semiconductor device, which is capable of reducing the reflectance of a metal in a visible region to a flat reflectance as low as possible so as to obtain a blackened color tone when viewed from an eye, Which is capable of forming a fine pattern by means of a metal layer, and has an optimum absorption layer having conductivity corresponding to a metal layer of low resistance, a method for producing the same, and an electronic apparatus.

According to the laminate of the present invention, the metal layer has a transparent substrate, a metal layer formed on the substrate, and a metal compound layer formed on at least one side of the metal layer so as to be in contact with the surface, Cm < 2 > and having a resistivity of 10 mu OMEGA .cm or less, wherein the metal compound layer is made of a transparent oxide semiconductor material and a zinc (Zn ) And a metal having an oxide formation free energy equal to or higher than that of the metal.

Because of this structure, a transparent transparent oxide semiconductor material having conductivity and a metal having an oxide formation free energy equal to or higher than that of zinc (Zn) can be arbitrarily combined, and electric characteristics (conductivity), optical characteristics (refractive index and extinction coefficient extinction coefficient) and etching property (solubility in etchant, etch rate) can be freely controlled to a desired value.

Therefore, the electrical wiring connection to other metal wirings is easy, the good electrical conductivity is ensured, the reflectance of the metal surface from the view side is reduced, and at the same time, the blackening makes it possible to suppress glare caused by the metal layer, A conductive laminate capable of forming an arbitrary fine pattern can be achieved with a small number of layers.

The laminate of the present invention can improve the response speed when used for an electrode material for an electromagnetic device and can improve the visibility due to microfabrication and reduction of the reflectance, patterning by batch etching, Cost reduction can be achieved.

Further, since the metal compound layer is made of a transparent oxide semiconductor material and a mixture of a metal having an oxide formation free energy equal to or higher than that of zinc (Zn), the optical constants (refractive index, extinction coefficient and absorption) So that the design of the laminated body becomes easy. Further, a laminate having a light absorbing layer having good conductivity can be obtained.

In addition, since it is a layer which absorbs much as compared with the case where it is composed only of a compound such as a metal oxide, a metal nitride, a metal oxynitride and a metal carbide, the reflectance on the surface of the metal layer can be greatly reduced and only the metal layer and the one- Even if the two-layer structure constituted by the present invention is formed, the visibility of the laminate is reduced and the 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 displays of various display devices, devices requiring aesthetic appearance such as touch panels, and the like, and can be used for display devices, light emitting devices, , And other electronic devices.

The metal layer is made of 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 and a layer of an alloy containing the metal as a main component, When a wiring pattern is formed from a metal layer and a metal compound layer, the wiring pattern can be finely formed. Therefore, visibility can be maintained even when used in a touch panel or the like on the display surface.

The laminate of the present invention can form a batch pattern of a metal layer, a metal compound layer or a metal compound layer, a metal layer and a metal compound layer in a wet etching process, and a fine pattern of 4 占 퐉 is also possible. Therefore, it has a good function as a main electrode of a touch panel, a display element, a light emitting element, a photoelectric conversion element, or a connection electrode to an auxiliary electrode and a terminal.

A metal having oxide free energy equal to or higher than that of zinc (Zn) is a metal that can secure conductivity and is hardly oxidized. Therefore, by mixing a metal having an oxide formation free energy equal to or higher than that of zinc (Zn) in the metal compound layer, it is possible to effectively use the property that the absorption of the metal which is difficult to be oxidized is large.

Further, since not only the metal layer but also the metal compound layer are electrically conductive, it is possible to easily make electrical connection with other wiring, and it becomes possible to form a wiring pattern from the metal layer and the metal compound layer of the present invention and use it as a wiring.

In this case, the metal layer may be formed by laminating a layer of the at least one alloy and a dissimilar metal layer made of a metal different from the metal which is the main component of the alloy layer.

Because of this configuration, it is easy to adjust the characteristics such as the optical constant and the etching rate of the laminate.

The metal layer may include a single layer of copper (Cu), aluminum (Al), silver (Ag), or an alloy of these metals, a molybdenum (Mo) layer, a molybdenum alloy layer, an aluminum , And an aluminum alloy layer may be laminated on the second layer or the third layer.

Because of this structure, the metal layer can be made low resistance, and the wiring pattern can be finely formed in the case of forming the wiring pattern from the metal layer and the metal compound layer, so that the visibility can be maintained even when used on a touch panel or the like on the display surface.

The metal compound layer may have a refractive index n of 2.0 to 2.8 and an extinction coefficient k of 0.6 to 1.6 in a visible region (400 to 700 nm).

Because of such a constitution, the reflection is suppressed, and a dark colored laminate having no red, yellow or blue color can be formed.

In this case, the metal compound layer is 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₎ And a layer composed of a mixture of one or two kinds of transparent oxide semiconductor materials containing an additive as a main component and a metal having an oxide formation free energy equal to or higher than that of zinc (Zn).

With this configuration, it is possible to construct a laminated body of a dark color having no red, yellow, or blue color with a small difference in average reflectance, maximum reflectance and minimum reflectance in the visible region.

When two kinds of transparent oxide semiconductor materials are used for the metal compound layer, the optical constants and the etching rate of the laminate can be widely selected by changing the ratio of the two kinds of transparent oxide semiconductor materials.

At this time, the metal having an oxide formation free energy equal to or higher than that of the zinc (Zn) is Zn, Cu, Ni, Mo, Co, Pb, And at least one kind of metal selected from the group consisting of

As described above, since these metals which can secure conductivity and can not be 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 lowered.

In this case, the metal compound layer may be formed by mixing the transparent oxide semiconductor material and a metal having an oxide formation free energy equal to or higher than zinc (Zn) at a volume ratio of 8: 2 to 5: 5.

As a result, it is possible to optimize the optical constants (refractive index, extinction coefficient and absorption) as well as securing the conductivity. Thus, the average reflectance in the visible region, the redness in the difference between the maximum reflectance and the minimum reflectance, It is possible to constitute a laminated body of a dark color free from blue, violet, or the like.

The metal compound layer may include at least one selected from the group consisting of oxygen (O), nitrogen (N), and carbon (C), and the thickness of the metal compound layer may be in the range of 30 nm to 60 nm.

By adjusting the amount of nitrogen, oxygen or carbon in the metal compound layer, the optical constants (refractive index, extinction coefficient, absorption) of the metal compound layer constituting the laminate can be appropriately controlled. Further, nitrogen, oxygen, or carbon in the metal compound layer has the function of adjusting the conductivity and the etching property (etching rate) together, so that it can be adjusted to the optimum film quality electrically, optically and chemically. Further, the range of the etching characteristics and optical characteristics can be adjusted by the reactive gas to be contained, and it becomes possible to use more kinds of metal or transparent oxide semiconductor material in the metal compound layer. It is also possible to form a laminate of a metal compound layer and a metal layer in a fine pattern.

Further, when the metal compound layer is formed on the opposite side of the substrate of the metal layer, the surface of the laminate is covered with a conductive material composed of nitride, oxide or carbide of metal, so that a laminate having excellent environmental resistance can be obtained.

It is also possible to arbitrarily combine any one or more of oxygen (O), nitrogen (N) and carbon (C) with a transparent transparent oxide semiconductor material having conductivity, a metal having an oxide formation free energy equal to or higher than that of zinc (Zn) It is possible to freely control electric characteristics (conductivity), optical properties (refractive index and extinction coefficient), and etching properties (solubility in etchant, etch rate) to desired values.

Therefore, it is possible to suppress glare caused by reducing the reflectance (low reflectance and blackening) of the metal surface from the view side while ensuring good electrical conductivity by facilitating electrical wiring connection to other metal wiring, and further, It is possible to secure a conductive laminate capable of forming arbitrary fine patterns collectively by a small layer structure.

The laminate of the present invention can improve the response speed when used for an electrode material for an electromagnetic device and can improve the visibility due to microfabrication and reduction of the reflectance, patterning by batch etching, Cost reduction can be achieved.

At this time, in the visible range (400 to 700 nm), the reflectance for light incident from the metal compound layer side of the laminate is 1.0% or more and 15% or less on average, and the difference between the maximum reflectance and the minimum reflectance is 10% or less. It may be dark.

Because of such a constitution, the glare of the laminate is reduced and the 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 displays of various display devices, touch panels, and other devices requiring aesthetic appearance, and can be suitably used for displays, light emitting devices, touch panels, And other electronic devices.

It is important to select a material that becomes as small as possible to be a difference between the maximum reflectance and the minimum reflectance in order for the laminate to exhibit a darker color. In the present invention, since the difference between the maximum reflectance and the minimum reflectance is adjusted to be 10% or less, A dark colored laminate can be obtained.

At this time, the laminate of the present invention may be provided, and the metal layer and a metal compound layer formed on at least one side of the metal layer so as to be in contact with the surface may be formed on at least a part of the substrate or in a pattern.

The laminate of the present invention can be suitably used for displays of various display devices, touch panels, and other devices requiring aesthetically pleasing appearance, and is suitable for display devices, light emitting devices, touch panels, solar cells , And other electronic devices.

According to the above-described method for producing a laminate of the present invention, it is possible to form a layer of at least one layer of a metal having a resistivity of 1.0 mu OMEGA .cm to 10 mu OMEGA. Cm or an alloy containing the metal as a main component on a transparent substrate, At least one of a transparent oxide semiconductor material and at least one kind of metal having an oxide formation free energy equal to or higher than that of zinc (Zn) in at least one of the metal layer forming step and the metal layer forming step, Or more of the above-mentioned mixture is formed, and a metal compound layer forming step of forming a metal compound layer which is a light absorbing layer having conductivity is performed.

Since the metal compound layer is made of a transparent oxide semiconductor material and a mixture of metals having an oxide formation free energy equal to or higher than that of zinc (Zn), it is desired to appropriately optimize optical constants (refractive index, extinction coefficient and absorption) So that the design of the laminated body becomes easy.

In addition, since it is a layer which absorbs much as compared with the case where it is composed only of a compound such as a metal oxide, a metal nitride, a metal oxynitride and a metal carbide, the reflectance on the surface of the metal layer can be greatly reduced and the metal layer and one metal compound layer Even if the two-layer structure is constituted by only the single layer structure, the 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 displays of various display devices, touch panels, and other devices requiring aesthetic appearance, and can be suitably used for displays, light emitting devices, touch panels, And other electronic devices.

The metal layer is made of 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 and a layer of an alloy containing the metal as a main component, In the case of forming a wiring pattern using a metal layer and a metal compound layer, the wiring pattern can be finely formed, and visibility can be maintained even when used on a touch panel or the like on the display surface.

According to the present invention, it is possible to arbitrarily combine a transparent transparent oxide semiconductor material having conductivity and a metal having an oxide formation free energy equal to or higher than that of zinc (Zn) And dissolution coefficient) and the etching property (solubility in etchant, etching rate) can be freely controlled to a desired value.

Therefore, the electrical wiring connection to other metal wirings is easy, the good electrical conductivity is ensured, the reflectivity of the metal surface from the visual side is reduced, and the blackening is suppressed to suppress glare caused by the metal layer, It is possible to achieve a conductive laminate capable of forming a fine pattern with a small number of layers.

The laminate of the present invention can improve the response speed when used for an electrode material for an electromagnetic device and improve the visibility due to microfabrication and reduction of the reflectance, patterning by batch etching, Cost reduction can be achieved.

1 is a schematic cross-sectional view of a layered product 1 according to an embodiment of the present invention.
Fig. 2 is a graph showing measured values of the refractive index at 400 to 700 nm of the substrate on which the metal compound layer is formed in Examples 1 to 4, in which the metal compound layer is formed by changing the ratio of ZnO and Cu.
Fig. 3 is a graph showing calculation values of the extinction coefficient of the metal compound layer-adhered substrates of Examples 1 to 4 in which the metal compound layer is formed by changing the ratio of ZnO to Cu.
Fig. 4 is a graph showing measured values of reflectance of the laminate of Examples 1 to 4 in which a metal layer made of Cu is formed by forming a metal compound layer by changing the ratio of ZnO and Cu.
5 is a graph showing the difference between the average reflectance and the maximum reflectance and the minimum reflectance of the laminate of Examples 1 to 4 in which a metal layer made of Cu is formed by changing the ratio of ZnO and Cu to form a metal compound layer.
6 is a graph showing the refractive indexes of the substrates with a metal compound layer of Examples 5 to 14 in which a Zn-Cu (5: 5) metal compound layer is formed by changing the amount of introduction of nitrogen or oxygen.
7 is a graph showing the extinction coefficient of the substrates with metal compound layers of Examples 5 to 14 in which a Zn-Cu (5: 5) metal compound layer is formed by changing the amount of introduction of nitrogen or oxygen.
8 is a graph showing measured values of reflectance of the laminated bodies of Examples 5 to 14 in which a metal layer made of Cu is formed after forming a Zn-Cu (5: 5) metal compound layer by changing the amount of introduction of nitrogen or oxygen.
9 shows the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminate of Examples 5 to 14 in which a metal layer made of Cu is formed after forming a Zn-Cu (5: 5) FIG.
10 is a graph showing measured values of the reflectance of the laminate of Examples 15 to 19 in which a metal layer made of Cu is formed by forming a metal compound layer by changing the ratio of In ₂ O ₃ and Mo.
11 is a graph showing the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminate of Examples 15 to 19 in which a metal layer is formed by forming a metal compound layer by changing the ratio of In ₂ O ₃ to Mo .
12 is a graph showing measured values of the reflectance of the laminate of Examples 21 to 25 in which a metal layer made of Cu is formed after the metal compound layer is formed by changing the ratio of ZnO-Cu and In ₂ O ₃ .
Figure 13 is representing the difference of the ZnO-Cu and In ₂ O after film formation of the metal compound layer by changing the ratio of _3, and the average reflectance and the maximum reflectance and the minimum reflectance of the laminate of the embodiment by forming the metal layer made of Cu for example, 21-25 Graph.
14 is a graph showing measured values of reflectance of a laminate of Examples 26 to 30 in which a metal layer made of Cu is formed by forming a metal compound layer by changing the ratio of ZnO-Cu and SnO ₂ .
Figure 15 is a graph showing the difference in the ZnO-Cu and SnO after film formation of the metal compound layer by changing the ratio of _2, and the average reflectance and the maximum reflectance and the minimum reflectance of the laminate of the embodiment by forming the metal layer made of Cu for example, 26-30 .
16 is a graph showing measured values of reflectance of the laminated bodies of Examples 31 to 36 in which a metal layer made of Cu is formed by forming a metal compound layer of ZnO-Cu and SnO ₂ by changing the amount of nitrogen introduced.
17 is a graph showing the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminate of Examples 31 to 36 in which a metal layer made of ZnO-Cu and SnO ₂ is formed by changing the amount of nitrogen introduced and a metal layer made of Cu is formed to be.
18 is a graph showing measured values of reflectivities of the laminated bodies of Examples 37 to 41 in which a metal compound layer of ZnO and Cu is formed by changing the amount of nitrogen introduced and a metal layer of a two-layer structure of a MoNb film and an AlNd film is formed.
19 shows the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminate of Examples 37 to 41 in which the metal compound layer of ZnO and Cu is formed by changing the amount of nitrogen introduced and the metal layer of the MoNb film and the AlNd film is formed, FIG.
20 is a graph showing measured values of reflectance of laminated bodies of Examples 42 to 47 in which a metal layer made of an AlNd film or an APC film is formed by forming a metal compound layer of ZnO and Cu by changing the film thickness.
21 shows the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminate of Examples 42 to 47 in which a metal layer made of an AlNd film or an APC film was formed after forming a metal compound layer of ZnO and Cu by changing the film thickness Graph.
Fig. 22 is a graph showing the results of a comparison between the case where a metal compound layer in which a ZnO ratio is changed from 1 to 5 to two kinds of metals (Ni: Cu = 1: 1) having an oxide formation free energy equal to or greater than Zn is formed, 54 to 58 are graphs showing the average reflectance and the difference between the maximum reflectance and the minimum reflectance.
23 is a graph showing the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminate of Examples 54, 59 and 60 in which the oxygen flow rate was changed when the metal compound layer made of Ni: Cu: ZnO = 1: 1: to be.
24 is a graph showing measured values of the reflectance of the laminate in Examples 54 to 60 of Figs. 22 and 23. Fig.
Figure 25 is one kind of metal (Mo) and oxide (ZnO + Al ₂ O ₃₎ a first ratio of: 2, and the ratio of ZnO and _{Al 2 O 3 (5: 1} ), (4.5: 1.5), (4 : 2), thereby obtaining the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminate of Examples 61 to 63 in which the metal compound layer was formed in 50 nm.
26 is a graph showing the relationship between the ratio of one kind of metal (Mo) and the oxide (ZnO + Al ₂ O ₃ ) of 1: 2 and the ratio of ZnO and Al ₂ O ₃ (5: : 2), and the metal compound layers were formed to a thickness of 50 nm.
27 is a ZnO: one embodiment of forming the metal layer comprising a metal compound layer (50 nm) of 1.5 in the film formation, Cu or Al for example, 64,65: one type of metal (Mo): Al ₂ O ₃ ratio of 4.5: 3 The average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminate.
28 is a ZnO: one embodiment of film formation of the metal layer comprising a metal compound layer (50 nm) of 1.5 in the film formation, Cu or Al for example, 64,65: one type of metal (Mo): Al ₂ O ₃ ratio of 4.5: 3 FIG. 5 is a graph showing measured values of the reflectance of the laminate. FIG.
Fig. 29 shows the result of forming a metal compound layer (interval of 5 nm between 40 nm and 60 nm) at a ratio of ZnO: one kind of metal (Mo): Al ₂ O ₃ of 4.5: 3: 1.5, And the minimum reflectance of the laminate of Examples 66 to 70 in which the film thickness (100 nm) was formed.
30 shows the result of forming a metal compound layer (interval of 5 nm between 40 nm and 60 nm) at a ratio of ZnO: one kind of metal (Mo): Al ₂ O ₃ of 4.5: 3: 1.5, (100 nm) is formed on the surface of the laminate of Examples 66 to 70.
31 is a ZnO: Cu = 1: 1 and the ratio of _{Al 2 O 3 (ZnO: Cu} ) :( Al 2 O 3) = 10: 3.5 to between the metal compound layer (35 nm ~ 65 nm 15 nm interval) A graph showing the difference between the average reflectance and the maximum reflectance and the minimum reflectance of the laminated bodies of Examples 71 to 73 in which Cu was formed as a metal layer after film formation.
32 is a ZnO: Cu = 1: 1 and the ratio of _{Al 2 O 3 (ZnO: Cu} ) :( Al 2 O 3) = 10: 3.5 to between the metal compound layer (35 nm ~ 65 nm 15 nm interval) Of the laminate of Examples 71 to 73 in which Cu is deposited as a metal layer after film formation.

BEST MODE FOR CARRYING OUT THE INVENTION The laminate of one embodiment of the present invention will be described in detail below with reference to the drawings.

≪ Structure of the layered product (1)

The layered product 1 of the present embodiment can be used in a display device such as a liquid crystal display or a plasma display inserted in various electronic apparatuses such as a cellular phone, a portable information terminal, a game machine, a ticket machine, an ATM device and a car navigation system And is used as a substrate. In addition, it can be used as a main electrode such as a display element, a light emitting element, a photoelectric conversion element, or a connection electrode of an auxiliary electrode and a terminal.

The laminate 1 of the present embodiment is formed by sequentially forming a metal compound layer 30a, a metal layer 20 and a metal compound layer 30b on a transparent substrate 10 as shown in Fig.

However, the layered product 1 of the present embodiment may be configured not to include the metal compound layer 30b depending on the application to which it is applied. In this case, a metal layer 20 is formed on the transparent substrate 10, and a metal compound layer 30a having conductivity, which is a metal compound layer, is formed between the transparent substrate 10 and the metal layer 20. [

The laminate 1 of the present embodiment is constructed so as not to include the metal compound layer 30a and the metal layer 20 is formed directly on the transparent substrate 10. The metal compound layer 30b is formed on the metal layer 20 .

The substrate 10 is a well-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 is formed by providing a single layer or a plurality of layers of a metal having a resistivity of 1.0 mu OMEGA .cm to 10 mu OMEGA .cm or an alloy having a resistivity of 1.0 mu OMEGA .cm to 10 mu OMEGA. Cm as a main component.

A metal such as silver (Ag), copper (Cu), or aluminum (Al) is used as a metal having a specific resistance of 1.0 μΩ · cm to 10 μΩ · cm. Since the laminate 1 is used as an electrode, a metal material capable of freely forming a pattern due to its low resistance value is suitable as a material of the metal layer 20, especially when a high resistance value is specified and used, to be.

The metal layer 20 may be made of an alloy of a metal such as Ag, Cu, or Al.

Molybdenum (Mo), nickel (Ni), an alloy thereof, or the like may be used as a material of the metal layer 20 in order to efficiently reduce the reflectance in combination with the metal compound layers 30a and 30b.

However, in consideration of conductivity and etching property, Cu is a more effective material in terms of conductivity and etching property when used for the metal layer 20.

The metal layer 20 is adjusted so that the resistivity of the entire layer is 10 mu OMEGA .cm or less.

The metal layer 20 is formed of a single layer made of a metal having a resistivity of 1.0 μΩ · cm to 10 μΩ · cm such as Ag, Cu, or Al or an alloy thereof, and a heterogeneous layer made of a metal different from the metal A metal layer may be laminated. For example, a single layer made of a metal such as Ag, Cu, Al or an alloy thereof, and two or more layers each containing a different metal from the one layer and composed of any one of Mo, Mo alloy, Al and Al alloy .

The metal compound layers 30a and 30b of the present embodiment are a light absorbing layer having conductivity and made of a transparent oxide semiconductor material and a mixture of at least one kind of metal having an oxide formation free energy equal to or higher than that of zinc (Zn).

The transparent oxide semiconductor material may be any one or two kinds of transparent oxide semiconductor materials containing indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO ₂ ) Or a dielectric, metal oxide, metal nitride, metal oxynitride, metal carbide or the like having a refractive index (n) of 1.7 to 2.7 equivalent to these may be used. However, since the metal compound layers 30a and 30b require conductivity, a transparent oxide semiconductor material may be used.

The metal having oxide free energy equal to or higher than that of zinc includes copper (Cu), nickel (Ni), molybdenum (Mo), cobalt (Co), lead (Pb) As a standard free energy of oxide formation, it is possible to select a metal which is equal to or higher than Zn in an Euling diagram of a typical oxide.

The metal to be mixed with the metal compound layers 30a and 30b is a metal having an oxide formation free energy equal to or higher than that of zinc (Zn). When a metal having a lower oxide formation free energy than Zn is used, It is difficult to obtain a thin film having an appropriate optical constant with a large absorption which is intended to act only as a simple additive of the transparent oxide semiconductor material.

Further, a metal having an oxide formation free energy equal to or higher than that of zinc (Zn) is mixed with the metal compound layers 30a and 30b for the following reason.

That is, the metal layer 20 is a layer for securing main conductivity, and the metal compound layers 30a and 30b are layers for reducing glare caused by high reflectance of the metal layer 20 due to gloss. Therefore, it is necessary to suitably absorb the reflection of the metal in the metal compound layers 30a and 30b. When the metal compound layers 30a and 30b are formed of a transparent oxide semiconductor material, a dielectric material, or a variety of metal compounds, the effect of reducing the reflectance can not be sufficiently obtained because these materials are less absorbed. In this case, since a single layer of the metal compound layers 30a and 30b is insufficient, a semi-permeable layer of metal may be separately disposed between the metal layer 20 and the metal compound layers 30a and 30b, or alternatively, So that it becomes necessary to laminate them.

The metal compound layers 30a and 30b made of transparent oxide semiconductor materials or dielectrics or various metal compounds can be formed only by controlling the temperature, pressure, rate, plasma or reaction gas at the time of film formation to reduce reflectance, flatness of visible spectral characteristics, , And etchability can not be expected, and thus can not be a single layer of a laminate having a sufficient function.

Thus, in the present embodiment, by mixing the metal compound layers 30a and 30b with a metal having oxide free energy equal to or higher than that of zinc (Zn), it is possible to reduce the reflectance, the flatness of the spectral characteristics in the visible range, It is now possible to obtain performance. Therefore, a semi-permeable layer of metal is also unnecessary.

The metal compound layers 30a and 30b of the present embodiment have a refractive index n of 1.5 to 3.0 in the visible range (400 to 700 nm), an extinction coefficient (k) of 0.30 to 2.5 and a film thickness of 30 to 60 nm Absorption (?) In the range of 20 to 60%.

In order to reduce the reflectance and to show a change when viewed with eyes, the shape of the graph in the range of the visible range with the spectral reflectance on the vertical axis as the wavelength and the wavelength on the horizontal axis as the wavelength on the vertical axis It is necessary to make it as flat as possible and to reduce the reflectance in the entire visible range.

The volume ratio of the transparent oxide semiconductor material and the metal having the oxide formation free energies equal to or higher than that of zinc (Zn) in the metal compound layers 30a and 30b is equal to or higher than that of the transparent oxide semiconductor material: zinc (Zn) Is in the range of 8: 2 to 5: 5. Thus, both the conductivity, the optical constant and the etching property of the metal compound layers 30a and 30b can be set within a suitable range.

Further, since two kinds of transparent oxide semiconductor materials are used in combination and two kinds of metals having oxide free energy equal to or higher than that of zinc (Zn) are mixed and used, the combinations of materials are enriched, so that reflectance, Can be finely controlled.

The metal compound layers 30a and 30b can be formed into a film having good conductivity and etching property by introducing at least one of oxygen (O ₂ ), nitrogen (N ₂ ), and carbon dioxide (CO ₂ ) at the time of film formation.

By selecting a combination of the optical constant and the film thickness, the reflectance of the laminate 1 with respect to the light incident from the side of the metal compound layers 30a and 30b is set to a visible average of 1.0% or more and 15% or less, It is possible to form the layered product 1 which exhibits a dark color when viewed from the eyes.

≪ Method for producing layered product (1)

The layered product 1 of the present embodiment is a layered product 1 in which one layer or more of a metal having a resistivity of 1.0 mu OMEGA .cm to 10 mu OMEGA. Cm or an alloy mainly composed of the metal is formed on a transparent substrate 10 and a resistivity of 10 and at least one of a transparent oxide semiconductor material and at least one of a metal having an oxide formation free energies equal to or higher than that of zinc (Zn) in at least one of the metal layer forming step and the metal layer forming step, And a metal compound layer forming step of forming a metal compound layer (30a, 30b) as a light absorbing layer having conductivity.

A method of manufacturing the layered product 1 of the present embodiment will be described below.

A metal compound layer forming step of forming a metal compound layer 30a, which is a light absorbing layer made of a mixture of a transparent oxide semiconductor material and a metal having an oxide formation free energy equal to or higher than that of zinc (Zn), is formed.

In this process, a target bonded with a transparent oxide semiconductor material, a target bonded with a metal having an oxide formation free energy equal to or higher than that of zinc (Zn), and a transparent substrate 10 are set in a sputtering apparatus, A target bonded with a transparent oxide semiconductor material so that a volume ratio of a metal film having an oxide formation free energy equal to or higher than that of zinc (Zn) is in a range of 8: 2 to 5: 5, a target bonded with a transparent oxide semiconductor material, The injected power of the target to which the metal having free energy is bonded is adjusted, and the metal compound layer 30a is blanket deposited by sputtering.

At this time, the transparent oxide semiconductor material may be sputtered in advance using a single target mixed with a metal having oxide free energy equal to or higher than that of zinc (Zn) in a volume ratio of 8: 2 to 5: 5, And a target in which a metal having an oxide formation free energy equal to or higher than that of zinc (Zn) is mixed in a volume ratio of 8: 2 to 5: 5 and an oxide having an oxide equal to or higher than other transparent oxide semiconductor material and / or zinc (Zn) A blanket film may be formed using a metal target having a free energy of formation.

Next, a metal layer forming step is performed in which 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 the metal are formed and a metal layer having a resistivity of 10 μΩ · cm or less is formed.

In this process, a film of a metal having a resistivity of 1.0 μΩ · cm to 10 μΩ · cm or an alloy containing the metal as a main component is formed by sputtering by a known method to a film thickness of about 120 nm. In addition, a metal having a resistivity of 1.0 mu OMEGA .cm to 10 mu OMEGA .cm or an alloy containing the metal as a main component is sputtered by a known method to form a film. Then, another metal having a resistivity of 1.0 mu OMEGA .cm to 10 mu OMEGA. As a main component may be sputtered by a known method to form a metal layer 20 composed of two layers. Alternatively, a multilayer film of three or more layers may be formed.

A metal compound layer forming step of forming a metal compound layer 30b, which is a light absorbing layer made of a mixture of a transparent oxide semiconductor material and a metal having an oxide formation free energy equal to or higher than that of zinc (Zn), is formed.

This step is performed according to the procedure of the metal compound layer forming step for forming the metal compound layer 30a.

According to the above procedure, the formation of the layered product 1 of the present embodiment is completed.

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 these steps, Either one of the steps may be performed.

Example

Hereinafter, the present invention will be described in more detail based on concrete examples. However, the present invention is not limited to the embodiments of the following embodiments.

(Test Example 1: Examination of ratio of transparent oxide semiconductor material to metal in metal compound)

In this 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 a transparent substrate 10 made of a glass substrate, The laminate 1 of Examples 1 to 4 in which the ratio of Cu was changed in four steps of 8: 2, 7: 3, 6: 4 and 5: 5 was examined for optical properties.

First, on a transparent substrate 10 made of a transparent glass substrate, a target bonded with a commercially available transparent oxide semiconductor material ZnO containing ZnO as a main component and a target of Cu-bonding a metal having a high oxide formation free energy are set in a sputtering apparatus (ZnO: Cu) of 8: 2 (Example 1), 7: 3 (Example 2), 6: 4 (Example 3), and 5: 5 A metal compound layer 30a of Examples 1 to 4 was prepared.

The sputtering conditions were as follows: no heating, a final pressure of 5.00E-4Pa, a sputtering pressure of 4.40E-1Pa, a DC input power of 1.66-0.75kw for a ZnO target, 0.11-0.2kw for a Cu target, The metal compound layer 30a was formed as a target.

The film thickness of the formed metal compound layer 30a was 37.2 to 44.7 nm.

(N) and the extinction coefficient (k) of the metal compound layer were calculated from the measured values of film thickness, transmittance, reflectance and refractive index of the substrate.

The measured values of the refractive index and the calculated values of the extinction coefficient are shown in Figs.

2 and 3, the resistivity was 7.32 E-2 to 4.58 E + 0? 占 ㎝ m, the refractive index was 2.17 to 2.7 in the visible range (400 nm to 700 nm), and the extinction coefficient was 0.475 to 1.53.

Next, Cu was deposited to a thickness of 120 nm on the thin film of each of the metal compound layers 30a of Examples 1 to 4 by the DC sputtering method, and the reflectance from the back side (glass side) was measured to obtain a visible range (400 nm to 700 nm, the difference between the maximum reflectance and the minimum reflectance was calculated. Also, in calculating the average reflectance and the maximum reflectance and the minimum reflectance difference, the value of reflectance canceled the reflectance of the glass surface as the light incident surface.

The results are shown in Fig. 4 and Fig.

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

The reason why the reflectance at 700 nm in Example 1 is high is because the film thickness of the metal compound layer is thin and the refractive index is low and the extinction coefficient is small as compared with the other Examples 2 to 4. [

In Example 1, it was confirmed that the maximum reflectance was 8.33%, the average reflectance was 4.08%, and the maximum and minimum reflectance difference were 6.57% by shifting the film thickness to 50 nm by calculating from the calculated refractive index and extinction coefficient.

With respect to optical constants, it was found that the refractive index increases as the proportion of Cu in the metal compound layer 30a increases from 20% to 50%, and the extinction coefficient also tends to increase.

It was also found that the refractive index and the extinction coefficient increase as the wavelength increases from 400 nm to 700 nm. This is attributed to the fact that the reflectance of Cu is high in the long wavelength region and the reflectance is low in the short wavelength region with the vicinity of 550 nm as the boundary due to the optical constant of Cu (in particular, the extinction coefficient k).

In Example 1, the difference between the maximum reflectance and the minimum reflectance was as large as 24.69%, resulting in a reddish reflection. In Example 4, the proportion of Cu in the film was high, so the refractive index of 500 nm to 700 nm was high and the extinction coefficient was high have. As a result, the reflectance at the long wavelength side is high and the reflectance at the short wavelength side is low. It was found that the ratio of ZnO to Cu was 7: 3 in Example 2 and 6: 4 in Example 3, and the refractive index was in the range of about 2.17 to 2.54 and the extinction coefficient was 0.66 to 1.20.

(Test Example 2: Nitrogen gas dependency)

In this example, the influence of the nitrogen gas introduced amount on the optical characteristics was examined in the case of forming the metal compound layer 30a by sputtering using ZnO as the transparent oxide semiconductor material.

A target in which a transparent oxide semiconductor material ZnO and Cu, which is a metal having a high free energy of oxide formation, were mixed at a volume ratio of 5: 5 by the same procedure as in Example 4 of Test Example 1 was produced.

Using this target, nitrogen gas was supplied at flow rates of 0 sccm (Example 5) and 10 sccm (Example 6) at a flow rate of 0 sccm (Example 5), a flow rate of 10 sccm (Example 6), and a flow rate of 10 sccm at a flow rate of 8.00E-4Pa, a sputtering pressure of 1.60E-1Pa, (Example 7), 20 sccm (Example 7), 30 sccm (Example 8), 40 sccm (Example 9), 50 sccm (Example 10), 60 sccm (Example 11), and 100 sccm (Example 12) A metal compound layer 30a was formed with a target thickness of 40 nm.

Further, instead of the nitrogen gas, oxygen gas was introduced at a flow rate of 5 sccm (Example 13) and 10 sccm (Example 14) to form the same film.

The refractive index n and the extinction coefficient k of the metal compound layer 30a were calculated from the film thickness, transmittance, reflectance and refractive index of the substrate for the metal compound layer 30a of Examples 5 to 14 in the same manner as in Test Example 1. [

The results are shown in Figs. 6 and 7. Fig.

6 and 7, in the metal compound layer 30a of Examples 5 to 14, the refractive index was in the range of 1.95 to 2.71 in the visible range (400 nm to 700 nm) and the extinction coefficient was in the range of 0.90 to 1.57 .

Next, Cu was deposited on the metal compound layer 30a of Examples 5 to 14 as the metal layer 20 of 120 nm by the DC sputtering method to prepare the layered product (1) of Examples 5 to 14. The reflectance of the layered product 1 of Examples 5 to 14 was measured from the back side (glass surface side) to calculate the difference between the average reflectance, the maximum reflectance and the minimum reflectance in the visible range (400 nm to 700 nm).

The results of measurement of the reflectance of the layered product (1) of Examples 5 to 12 are shown in Fig. 8, and the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the layered product (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 10 sccm to 100 sccm of nitrogen flow rate in Examples 6 to 12, The difference between the maximum reflectance and the minimum reflectance was 5% or less when the nitrogen flow rate in Examples 7 to 12 was in the range of 20 sccm to 100 sccm and the oxygen flow rate in Example 14 was 10 sccm.

Further, the reflectance of the average reflectance of 10% or less and the difference between the maximum reflectance and the minimum reflectance of 2.5% or less exhibited a better reflectance in the range of nitrogen flow rate of 30 sccm to 60 sccm in Examples 8 to 11. The reason why the average reflectance is 10% or less and the difference between the maximum reflectance and the minimum reflectance is 2.5% or less is that the reflectance is sufficiently suppressed at an average reflectance of 10% or less and the difference between the maximum reflectance and the minimum reflectance is 2.5% The dark color without red, yellow, blue, etc. is obtained.

As for the refractive index and the extinction coefficient, in Examples 7 to 12 and 14, the refractive index was in the range of 2.17 to 2.71 and the extinction coefficient was in the range of 0.9 to 1.57. In Examples 8 to 11 showing lower reflectivity and darkness, Of 2.25 to 2.66 and an extinction coefficient of 1.20 to 1.57.

In addition, even when oxygen gas was introduced at the time of sputtering, the average reflectance was reduced from 10% to 4% at an oxygen flow rate of 10 sccm of Example 14 compared to the oxygen flow rate of 5 sccm of Example 13, and the maximum reflectance and the minimum reflectance , The refractive index and the extinction coefficient can be controlled by selecting the optimum introduced gas amount, and it is possible to fabricate the laminate 1 which exhibits low reflection and dark color Could know.

(Test Example 3: Examples of other constituent materials 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 Mo is substituted for Cu as a metal having a high free energy of oxide formation .

A target bonded with a transparent oxide semiconductor material containing In ₂ O ₃ as a main component and a target bonded with Mo were set in a sputtering apparatus and the volume ratio of transparent oxide semiconductor material: Mo was 10: 1 (Example 15) The input power was changed so as to be 10: 2 (Example 16), 10: 3 (Example 17), 10: 4 (Example 18), 10: 5 (Example 19), and 10:10 And metal compound layers 30a of Examples 15 to 19 were fabricated.

The sputtering conditions were such that the DC input power of the transparent oxide semiconductor material was in the range of 0.18 kW to 0.46 kW and the DC input power of Mo was 0.1 kW to 0.45 kW in the Ar atmosphere with no heating, a pressure of 8.00E-4Pa, a sputter pressure of 1.60E-1Pa, kW, a metal compound layer 30a was formed by a 2-point sputtering with a film thickness of 40 nm as a target.

Subsequently, Cu was deposited to a thickness of 120 nm on the thin film of the metal compound layer 30a of each of Examples 15 to 19 by the DC sputtering method, and the reflectance from the back side (glass surface side) was measured to determine the visible range (400 nm to 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, the maximum reflectance and the minimum reflectance is shown in Fig.

The average reflectance of 15% or less and the difference between the maximum reflectance and the minimum reflectance were 10% or less in Examples 17 and 18 in which the transparent oxide semiconductor material and the DC input power ratio of Mo were 10: 3 and 10: 4. In Example 17, the average reflectance was 11.56%, the difference between the maximum reflectance and the minimum reflectance was 3.40%, in Example 18, the average reflectance was 14.02%, and the difference between the maximum reflectance and the minimum reflectance was 3.13%.

The average reflectance was as high as about 17% (weak) for Examples 16 and 19 of 10: 2 and 5, but the difference between the maximum reflectance and the minimum reflectance was 3.71% and 4.16%, and apparently dark color was shown.

(Test Example 4: Examination of constituent materials of metal compound layer)

In this example, the metal compound layer 30a made of an alloy of ZnO, Cu, and In ₂ O ₃ was formed by changing the ratio of ZnO, Cu, and In ₂ O ₃ , and examined for suitable ratios.

A target having a volume ratio of 5: 5 and an In ₂ O ₃ target in a ratio of ZnO as a transparent oxide semiconductor material and Cu as a metal having a high free energy of oxide formation was set in a sputtering apparatus and the volume ratio of ZnO · Cu mixture and In ₂ O ₃ Of the applied electric power so as to be 10: 1 (Example 21), 10: 2 (Example 22), 10: 3 (Example 23), 10: The metal compound layer 30a of Examples 21 to 25 was prepared.

Sputter conditions of the non-heating, the ultimate pressure 8.00 E-4Pa, sputtering pressure 1.60 E-1Pa, argon (Ar) atmosphere from a range of ZnO · Cu mixture target of a DC input power _{0.14 kw ~ 0.72 kw, In 2} O 3 target The metal compound layer 30a was formed by a 2-armed sputtering with a DC input power of 0.1 kw and a film thickness of 40 nm as a target.

Thereafter, Cu was deposited to a thickness of 120 nm on the thin film of the metal compound layer 30a of each of Examples 21 to 25 by the DC sputtering method, and the reflectance from the back side (glass side) was measured to obtain a visible range (400 nm to 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 of 15% or less and the difference between the maximum reflectance and the minimum reflectance were 10% or less in Examples 23 to 25 in which the ZnO / Cu mixed target and the In ₂ O ₃ target had a DC input power ratio of 10: 3 to 5. In Example 23, the average reflectance was 12.92%, the difference between the maximum reflectance and the minimum reflectance was 6.17%, the average reflectance was 11.79% in Example 24, the difference between the maximum reflectance and the minimum reflectance was 5.80%, the average reflectance was 9.38% The difference between the maximum reflectance and the minimum reflectance was 4.64%.

In the range of this test example, the difference between the average reflectance, the maximum reflectance and the minimum reflectance became smaller with an increase in the proportion of In ₂ O ₃ , and thus the laminate 1 having better optical characteristics in accordance with the object of the present invention was obtained .

(Test Example 5: Examination of constituent materials of metal compound layer)

In this example, use of SnO ₂ in In ₂ O ₃ instead of the test example 4, and, ZnO, Cu, and the metal compound layer (30a) made of an alloy of SnO ₂ film deposition by changing the ratio of ZnO and Cu and SnO _2, a suitable Ratio.

A SnO ₂ target was set in place of the In ₂ O ₃ target of Test Example 4 in a sputtering apparatus and the volume ratio of ZnO · Cu mixture and SnO ₂ was set to 10: 1 (Example 26), 10: 2 (Example 27) The metal compound layer 30a of each of Examples 26 to 30 was formed into a two-layered film by changing the ratio of applied electric power such that the ratio was 10: 4 (Example 28), 10: 4 (Example 29) Respectively.

The sputter conditions were such that a metal compound layer was formed by a 2-armed sputtering with a DC input power of 0.15 kW to 0.75 kW for the ZnO · Cu mixture target and a DC input power of 0.1 kW for the SnO ₂ target to a film thickness of 40 nm.

Thereafter, Cu was deposited to a thickness of 120 nm on the thin film of the metal compound layer 30a of each of Examples 21 to 25 by the DC sputtering method, and the reflectance from the back side (glass side) was measured to obtain a visible range (400 nm to 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.

The average reflectance was 15% or less, and the difference between the maximum reflectance and the minimum reflectance was 10% or less in Examples 28 to 30 in which the ZnO-Cu mixture target and the SnO ₂ target had a DC input power ratio of 10: 3 to 5.

In Example 28, the average reflectance was 13.12%, the difference between the maximum reflectance and the minimum reflectance was 6.17%, in Example 29, the average reflectance was 9.94%, the difference between the maximum reflectance and the minimum reflectance was 5.44% %, And the difference between the maximum reflectance and the minimum reflectance was 6.99%.

As in the case of using the target of In ₂ O ₃ of Test Example 4, the average reflectance decreases with the increase of the ratio of SnO _2. However, since the bottom occurs at the ratio of 10: 4 of Example 29, ₂ ratio of 10: 4 was appropriate.

(Test Example 6: Nitrogen gas dependence of two types of transparent oxide semiconductor materials)

In this example, in the case by a transparent oxide semiconductor material using two kinds of ZnO and SnO ₂ for forming a metal compound layer (30a) by sputtering, it was examined for effects introduced amount of nitrogen gas on the optical properties.

ZnO as a transparent oxide semiconductor material, Cu and SnO ₂ , which are metals having high free energy of oxide formation, at a volume ratio of 2: 3: 1 were prepared and set in a sputtering apparatus.

The sputter conditions were as follows: no heating, a pressure of 8.00E-4 Pa, a sputter pressure of 1.60E-1Pa, a DC input power of 0.3 kW, an Ar gas of 120sccm, nitrogen gas of 0 sccm (Example 31) 32), 40 sccm (Example 33), 60 sccm (Example 34), 80 sccm (Example 35), and 100 sccm (Example 36), respectively.

Thereafter, Cu was deposited on the metal compound layer 30a of each of Examples 31 to 36 as a metal layer 20 of 120 nm by DC sputtering method to prepare the layered product (1) of Examples 31 to 36. The reflectance of the layered product 1 of Examples 31 to 36 was measured from the back side (glass surface side), and the difference between the average reflectance, the maximum reflectance and the minimum reflectance in the visible range (400 nm to 700 nm) was calculated.

The results of measurement of the reflectance of the layered product (1) of Examples 31 to 36 are 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 reflectance was 15% or less, and the difference between the maximum reflectance and the minimum reflectance was 10% or less in the case of the nitrogen flow rates of 20 sccm to 100 sccm in Examples 32 to 36. In Example 32 (nitrogen 20 sccm), the average reflectance was 13.17%, the difference between the maximum reflectance and the minimum reflectance was 2.78%, the average reflectance was 2.54%, the difference between the maximum reflectance and the minimum reflectance was 6.76% Respectively. As the nitrogen flow rate increases, the average reflectance gradually decreases. On the contrary, the difference between the maximum reflectance and the minimum reflectance increases.

In Example 31 (nitrogen 0 sccm), the reflectance at a wavelength of 550 nm or more was 23% or more. This is because the characteristic of reflectance of Cu greatly influences.

In addition, since the reflectance was lowered as the amount of nitrogen introduced increased, it was found that Cu was nitrided when the metal compound was formed by nitrogen introduction.

(Test Example 7 Examination of the amount of nitrogen introduced into the metal compound layer in the case where the metal layer has a two-layer structure of a MoNb film and an AlNd film)

The influence of the nitrogen flow rate at the time of film formation of the metal compound layer 30a on the characteristics of the reflectance of the laminate (1) was examined in the case where the metal layer 20 of Fig. 1 has a two-layer structure of a MoNb thin film and an AlNd thin film.

A target having a volume ratio of 5: 5 of ZnO, which is a transparent oxide semiconductor material, and Cu, which is a metal having a high free energy of oxide formation, was prepared and set in a sputtering apparatus.

The sputtering conditions were set to no heating, a pressure of 8.00E-4 Pa, a sputter pressure of 1.60E-1Pa and a DC input power of 0.3 kW, and a flow rate of 20 sccm (Example 37) and 40 sccm Example 38), 60 sccm (Example 39), 80 sccm (Example 40), and 100 sccm (Example 41), respectively.

Thereafter, 25 nm of a molybdenum alloy (MoNb) was formed as a metal layer 20 on the metal compound layer 30a of Examples 37 to 41, followed by 100 nm of an aluminum alloy (AlNd) to form a MoNb film and an AlNd film A metal layer 20 composed of a two-layer structure was formed. The reflectance of the layered product 1 of Examples 37 to 41 was measured from the back side (glass surface side), and the difference between the average reflectance, the maximum reflectance and the minimum reflectance in the visible range (400 nm to 700 nm) was calculated.

18 shows the results of measurement of the reflectance of the layered product (1) of Examples 37 to 41, 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 in the case of the nitrogen flow rates of 60 to 100 sccm for the nitrogen flow rates of Examples 39 to 41, 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 difference between the average reflectance, the maximum reflectance, the minimum reflectance, the maximum reflectance and the minimum reflectance as the nitrogen flow rate at the time of forming the metal compound layer 30a increases from 20 sccm to 100 sccm , All of the values were lowered, showing better optical characteristics. From these results, it was found that Cu scattered from the target was nitrided by the introduction of nitrogen at the time of sputtering.

In the range of the flow rate of 20 sccm to 100 sccm, the reflectance is continuously decreased with the increase of the nitrogen flow rate. Even at the nitrogen flow rate of 100 sccm, which is the maximum flow rate of this example, the average reflectance, maximum reflectance, minimum reflectance, It was found that a laminate film having a better low reflectance was obtained by further increasing the amount of nitrogen introduced to 100 sccm or more since all of the values of the difference did not reach the bottom.

(Test Example 8: Examination of metal compound film thickness in the case where the metal layer is an AlNd film or an APC film)

The film thickness of the metal compound layer 30a is larger than that of the laminate 1 in the case where the metal layer 20 shown in Fig. 1 is made of an Al alloy (AlNd) film or an Ag alloy (APC: Ag-Pd- The effects on the characteristics were examined.

A target having a volume ratio of 5: 5 of ZnO, which is a transparent oxide semiconductor material, and Cu, which is a metal having a high free energy of oxide formation, was prepared and set in a sputtering apparatus.

A ZnO-Cu film, which is a metal compound, was sputtered in an atmosphere of a sputtering condition of no heating, a pressure of 8.00E-4Pa, a sputter pressure of 1.60E-1Pa and a DC input power of 0.3 kW, and an argon gas of 120sccm and nitrogen gas of 60sccm A film thickness of 40 nm, 50 nm, and 60 nm was formed to obtain a metal compound layer 30a.

Thereafter, 100 nm of an aluminum alloy (AlNd) or 100 nm of an Ag alloy (APC) is deposited as a metal layer 20 on the metal compound layer 30a having a film thickness of 40 nm, 50 nm, .

The case where the metal compound layer 30a had a film thickness of 40 nm, 50 nm and 60 nm and the metal layer 20 was AlNd were respectively Examples 42 to 44 and the film thickness of the metal compound layer 30a was 40 nm and 50 nm , 60 nm, and the metal layer 20 was APC, respectively.

The reflectance of the layered product 1 of Examples 42 to 47 was measured from the back side (glass surface side), and the difference between the average reflectance, the maximum reflectance and the minimum reflectance in the visible range (400 nm to 700 nm) was calculated.

The results of measurement of the reflectance of the layered product (1) of Examples 42 to 47 are 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 film thickness of 40 nm, the difference between the maximum reflectance and the minimum reflectance was 10.68%, while in Examples 43 to 47, the average reflectance was 6.22% to 11.0% Of the laminated body 1 was within the range of 4.36% to 6.71%, and the laminated body 1 having a suitable reflectance characteristic was obtained with a dark color even when viewed with eyes.

(Test Example 9: Evaluation of etchability)

In this example, the evaluation of the etching property of the layered product 1 produced 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) .

Sputtering was performed 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 100 sccm on a substrate 10 made of a glass substrate under the same conditions as in Examples 11 and 12 of Test Example 2, A metal layer 20 made of Cu having a thickness of 120 nm was formed on the metal compound layer 30a by sputtering to form the metal compound layer 30a of the laminate 1 of Examples 48 and 49, .

On the substrate 10 made of a glass substrate under the same conditions as in Example 6 of Test Example 2, sputtering was performed from a target in which ZnO and Cu were mixed at a volume ratio of 5: 5 at a nitrogen flow rate of 10 sccm to form a metal film having a thickness of 40 nm A 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 to obtain a layered product 1 of Example 50. [

On the substrate 10 made of PET film under the same conditions as in Example 11 of Test Example 2, sputtering was performed 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 to form a metal compound layer A metal layer 20 made of Cu having a thickness of 120 nm was formed on the metal compound layer 30a by sputtering to obtain a layered product 1 of Example 51. Then,

Sputtering was carried out on a substrate 10 made of PET film at a flow rate of nitrogen of 60 sccm using a target in which ZnO and Cu were mixed at a volume ratio of 5: 5 under the same conditions as in Example 6 of Test Example 2, A metal layer 20 made of Cu having a thickness of 120 nm was formed on the metal compound layer 30a by sputtering and further ZnO and Cu were mixed at a nitrogen flow rate of 60 sccm at a volume ratio of 5: 5 to form a metal compound layer 30b having a film thickness of 40 nm to obtain a layered product 1 of Example 52. [

The laminate of Examples 48 to 52 was subjected to two kinds of treatments of nitric acid / hydrogen peroxide (Ech-1, manufactured by Geomatech) and phosphoric acid / nitric acid / acetic acid (Ech-2, Etching was carried out using a cantilever.

In the etching procedure, the layered product (1) of Examples 48 to 52 was cut into 50 millimeters x 50 millimeters, respectively, and immersed in each etchant to control the liquid temperature so that the etching end time (end point) was confirmed.

The etching end points of Examples 48 to 50 using the glass substrate were all 20 seconds at the same time in the etchant of nitric acid-hydrogen peroxide system (Ech-1), 45 to 45 hours at the etchant of phosphoric acid, nitric acid- 50 seconds, which is twice as long as that of Ech-1.

The etching end points of Examples 51 and 52 using the film substrate were 17 to 18 seconds in the etchant of nitric acid-hydrogen peroxide system (Ech-1) and 38 to 44 in the etchant of phosphoric acid, nitric acid- The result was somewhat faster, although it was about 10% higher than in Examples 48 to 50 using a glass substrate.

(Test Example 10: Etching Evaluation of Test Pattern)

The test samples of 20 占 퐉, 10 占 퐉 and 4 占 퐉 were applied to a plate using the layered product 1 of Examples 48 to 52 prepared in the same manner as in Test Example 9 to prepare a nitric acid-hydrogen peroxide system (Ech-1 ) Etchant and a phosphoric 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 the etching, and the receding width is an average value of the difference between the measured values of the resist width and the pattern width in each resist width by 2, Is calculated.

As shown in Table 1, in the etchant of the nitric acid-hydrogen peroxide system (Ech-1), a recess (over etch) with an unilateral dimension of about 0.5 to 0.6 mu m on the side of the resist pattern occurs, A pattern based on 10 탆 and 4 탆 could be formed. It was a good pattern even when observed from either side of the front or back surface.

A 20 탆 pattern was confirmed in the etchant of the phosphoric acid-nitric acid-acetic acid system (Ech-2), but a pattern of 10 탆 and 4 탆 was not confirmed and the pattern of the metal layer 20 became an overhanging shape, .

However, by adjusting the concentration and mixing ratio of the etchant, it was found that a reliable pattern can be formed in any etchant.

(Test Example 11 Etching Evaluation of Test Pattern)

In this example, the layered product (1) produced under the condition of Example 30 (the volume ratio of ZnO · Cu mixture and SnO ₂ is 10: 5) of Test Example 5 was evaluated for the etching property.

Sputtering was carried out 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, whereby a metal compound layer 30a having a thickness of 40 nm And a metal layer 20 made of Cu having a thickness of 120 nm is formed on the metal compound layer 30a by sputtering and further sputtering is performed so that the volume ratio of the ZnO · Cu mixture and SnO ₂ is 10: 5, A metal compound layer 30b having a thickness of 40 nm was formed to obtain a layered product 1 of Example 53. [

Using the layered product (1) of Example 53, 20 parts by mass of etchant of nitric acid-hydrogen peroxide system (Ech-1) and 20 parts of etchant of iron chloride (Ech-3, A pattern of a test pattern of 占 퐉 was used for etching to confirm the pattern dimensions of the sample.

The results are shown in Table 2.

From the results shown in Table 2, it can be seen that the etchant of the nitric acid-hydrogen peroxide system (Ech-1) has a recession (over etch) of about 0.2 μm on one side with respect to the resist pattern and an etchant of Ech- It was possible to form a pattern based on 20 탆, 10 탆 and 4 탆 at a retraction of about 0.5 탆 (over etch). However, since the etching rate of the metal compound layers 30a and 30b is fast in the etchant of iron chloride (Ech-3), reflection by Cu is slightly observed at the edge of the pattern even when viewed from the front and back surfaces.

(Test Example 12: Example in which the metal compound layer is made of a mixture with two kinds of metals)

Two kinds of metal of Cu and Ni and a metal compound layer 30a made of ZnO were formed on the substrate 10 and then Cu was used as the metal layer 20. Then, First, an alloy target of Cu and Ni (1: 1) and two ZnO targets were set in the apparatus, and the output of each target was adjusted so that the ratio of Cu: Ni: ZnO = 1: 1: Five kinds of metal compound layers 30a having a thickness of about 55 nm were formed by a two-way sputtering.

The sputtering conditions were as follows: no heating, a final pressure of 5.00E-4Pa, a sputtering pressure of 4.3E-1Pa, a DC input power of 1.66-0.35 kW for a ZnO target and 0.2 kW for a Zn target and a film thickness of 55 nm in an argon gas atmosphere A metal compound layer 30a was formed. Next, another Cu target was formed on the metal compound layer 30a, and a metal layer 20 made of Cu with a film thickness of 120 nm was formed by sputtering to obtain a laminate of Examples 54 to 58. [

In addition, 2 sccm of oxygen and 4 sccm of oxygen were introduced at the time of film formation at a ratio of Cu: Ni: ZnO = 1: 1: 1 to obtain a laminate of Examples 59 to 60.

The reflectance of the laminate of Examples 54 to 60 was measured from the metal compound layer 30a side (glass surface side), and the difference between the average reflectance, the maximum reflectance and the minimum reflectance in the visible range (400 nm to 700 nm) was calculated. The average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminate of Examples 54 to 60 are shown in Figs. 22 and 23, and the results of the reflectance measurement are shown in Fig.

The reason why the average reflectance is 15% or less and the difference between the maximum reflectance and the minimum reflectance is 10% or less in the case of not introducing oxygen at the time of film formation is as shown in Fig. 23 because the ratio of Cu: Ni: ZnO is 1: 4, respectively.

In the case of not introducing oxygen at the time of film formation, the reflectance at the ratio of 1: 1: 1 in Example 54 and 1: 1: 5 in Example 58 did not reach the expected reflectance level of 15% or less. It is considered that the reflectance was increased because the absorption of the metal compound layer was decreased in Example 58 in which the oxide ratio was 1: 1: 5 in many cases.

On the other hand, when the ratio is 1: 1: 1, the reaction gases such as oxygen gas O ₂ = 2 sccm and 4 sccm were introduced during film formation in Examples 59 and 60 shown in Figs. 23 and 24, The average reflectance was 15.75%, the difference between the maximum reflectance and the minimum reflectance was 5.65%, the mean reflectance was 14.78% in Example 60, and the difference between the maximum reflectance and the minimum reflectance was 6.12%.

(Test Example 13: Example in which the metal compound layer is composed of one kind of metal (Mo) and two kinds of dielectrics)

The ratio of ZnO, aluminum oxide (Al ₂ O ₃ ) and Mo (5: 1: 3), (4.5: 1.5: 3) and (4: 2: 3) as the transparent oxide semiconductor material constituting the metal compound layer 30a ) Was prepared.

The oxide compound target was set in the apparatus and the metal compound layer 30a was formed with no sputtering under the conditions of no heating, an arrival pressure of 8.00E-4Pa, a sputter pressure of 1.60E-1Pa, an Ar gas of 120sccm and an input power of 0.3 kW, An AlNd alloy was laminated to a thickness of 120 nm to form a metal layer 20 to obtain a laminate of Examples 61 to 63. [

The reflectance of the laminate of Examples 61 to 63 was measured from the metal compound layer 30a side (glass surface side), and the difference between the average reflectance, the maximum reflectance and the minimum reflectance in the visible range (400 nm to 700 nm) was calculated. The difference between the average reflectance and the maximum reflectance and the minimum reflectance of the laminate of Examples 61 to 63 is shown in Fig. 25, and the measurement result of the reflectance is shown in Fig.

As shown in Fig. 25 and Fig. 26, the difference between the average reflectance and the maximum reflectance and the minimum reflectance in Examples 61 to 63 was 10% or less, and a good dark color film was obtained from the viewing side. A large difference in the percentage of ZnO and Al ₂ O ₃ have not been confirmed.

Further, in the case of Example 64 (a) in which 50 nm of Cu and Al were respectively formed on the metal compound layer 30a in which the ratio of ZnO, Al ₂ O ₃ and Mo of the Example 62 was 4.5: 1.5: 3 and the metal layer 20 had a two- , And 65 were obtained.

The difference between the average reflectance and the maximum reflectance and the minimum reflectance in Examples 64 and 65 was 10% or less. However, when the film thickness was 50 nm, the reflectance As shown in FIG. It is considered that this is because the peaks of the lowest reflectance which is the bottom of the reflectance deviate due to the influence of the refractive index and the extinction coefficient of Cu and Al. In the case of forming a Cu film, the difference between the average reflectance and the maximum reflectance and the minimum reflectance in Example 64 can be reduced by thinning 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: 4.5: 1.5: 3 in Example 62 was varied in the range of 40 nm to 60 nm at intervals of 5 nm was changed to AlNd alloy To form a metal layer 20 to obtain a laminate of Examples 66 to 70.

The reflectance of the laminate of Examples 66 to 70 was measured from the metal compound layer 30a side (glass surface side), and the difference between the average reflectance, the maximum reflectance and the minimum reflectance in the visible range (400 nm to 700 nm) was calculated. The difference between the average reflectance and the maximum reflectance and the minimum reflectance of the laminate of Examples 66 to 70 is shown in Fig. 29, and the result of measurement of the reflectance is shown in Fig.

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 was 15% or less. In FIG. 29, the film thickness dependency is obviously apparent. This can easily be expected even when the metal layer 20 is made of Cu as described above.

(Test Example 14: Example comprising a metal compound layer (ZnO: Cu = 1: 1) and one kind of metal oxide)

A target having a ratio of ZnO and Cu of 1: 1 and a target of Al ₂ O ₃ were set in the device as the transparent oxide semiconductor material constituting the metal compound layer 30a, and as the metal compound layer 30a (ZnO: Cu = 1: ) and the ratio of one kind of metal oxide _{(Al 2 O 3) (ZnO} -Cu) :( Al 2 O 3) = 10: 3.5 by adjusting the output of each of the sputtering power so that the film thickness of 35 nm, 50 nm , And 65 nm, respectively. Then, 120 nm of Cu was laminated as the metal layer 20 to obtain a laminate of Examples 71 to 73. [

The reflectance of the laminate of Examples 71 to 73 was measured from the metal compound layer 30a side (glass surface side), and the difference between the average reflectance, the maximum reflectance and the minimum reflectance in the visible range (400 nm to 700 nm) was calculated. The average reflectance and the difference between the maximum reflectance and the minimum reflectance of the stacked bodies of Examples 71 to 73 are shown in Fig. 31, and the results of measurement of the reflectance are shown in Fig.

In Examples 71 and 72 in which the metal compound layer 30a had a film thickness of 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 in which the metal compound layer 30a had a thickness of 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 had a film thickness of 35 nm, 50 nm, or 65 nm, the reflectivity with good flatness was obtained. In Example 73 in which the metal compound layer 30a had a film thickness of 65 nm, the reflectance as a whole visible range was a little high, and the difference between the maximum reflectance and the minimum reflectance was small.

In the case of a conventional laminate in which only a layer of a transparent oxide semiconductor material is combined with a metal layer, the reduction of the reflectance and the interference color due to the bottom are likely to become clear due to the relationship between the refractive index and the extinction coefficient. On the other hand, it has been found from the above-mentioned examples that it is possible to obtain a laminated film exhibiting a more desirable dark color by combining a metal layer made of a mixture of a metal and a metal having an oxide formation free energy equal to or higher than zinc oxide of the present invention.

1 laminate
20 metal layer
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 side of the metal layer so as to be in contact with the surface,
Wherein the metal layer is composed of a metal layer having at least one layer of a metal having a resistivity of 1.0 mu OMEGA .cm to 10 mu OMEGA .cm or an alloy containing the metal and having a resistivity of 10 mu OMEGA .cm or less,
Wherein the metal compound layer is formed of one or two kinds of transparent oxide semiconductor materials selected from the group consisting of indium oxide (In ₂ O ₃ ), zinc oxide (ZnO) and tin oxide (SnO ₂ ) And a mixture of at least one kind of metal. The method according to claim 1,
Wherein the metal layer is formed by laminating a layer of the at least one alloy and a dissimilar metal layer made of a metal different from the metal contained in the layer of the alloy. 3. The method of claim 2,
Wherein the metal layer comprises a single layer of copper (Cu), aluminum (Al), silver (Ag), or an alloy of these metals and a molybdenum (Mo) layer, a molybdenum alloy layer, an aluminum And a second layer or a third layer selected from the group consisting of aluminum alloy layers. The method according to claim 1,
Wherein the metal compound layer has a refractive index (n) of 2.0 to 2.8 in a visible range (400 to 700 nm) and an extinction coefficient (k) of 0.6 to 1.6. The method according to claim 1,
The metal having oxide free energy equal to or higher than that of zinc (Zn) includes zinc (Zn), copper (Cu), nickel (Ni), molybdenum (Mo), cobalt (Co), lead (Pb), and molybdenum alloy Wherein the metal is one or more kinds of metals selected from the group consisting of iron and iron. 6. The method of claim 5,
Wherein the metal compound layer is formed by mixing the transparent oxide semiconductor material and a metal having an oxide formation free energy equal to or greater than zinc (Zn) at a volume ratio of 8: 2 to 5: 5. The method according to claim 1 or 4,
Wherein the metal compound layer contains at least one of the group consisting of oxygen (O), nitrogen (N), and carbon (C)
Wherein the metal compound layer has a thickness of 30 nm to 60 nm. The method according to claim 1 or 4,
The reflectance for light incident from the side of the metal compound layer in the visible range (400 to 700 nm) of the laminate is 1.0% or more and 15% or less on average, and the difference between the maximum reflectance and the minimum reflectance is 10% or less, Laminate showing dark color. A laminated body according to any one of claims 1 to 4,
Wherein 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 in a pattern. A metal layer forming step of forming a metal layer having a resistivity of 10 占 占 m or less by forming at least one layer of a metal having a resistivity of 1.0 占 · m to 10 占 占 · m or an alloy including the metal on a transparent substrate,
The metal layer forming step I, indium (In ₂ O ₃₎ oxide, zinc oxide (ZnO) and tin oxide (SnO ₂₎ either one or two of the transparent oxide semiconductor materials of the zinc (Zn) according to at least one of the elements And a metal compound layer forming step of forming a metal compound layer which is a light absorbing layer having conductivity, is carried out by forming a film of at least one kind or more of a metal having an oxide formation free energy equal to or larger than that of the metal compound layer. delete

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