TWI595507B - Laminates, methods of making the same, and electronic machines - Google Patents

Description

Laminated body, method of manufacturing the same, and electronic machine

The present invention relates to a laminate which can be used for a metal electrode or the like for an electronic device or an optical device, and which is composed of a metal and a conductive metal compound, a method for producing the same, and an electronic device.

In recent years, the electrode used in various electronic devices such as liquid crystal and organic EL (including an auxiliary electrode for improving conductivity) has been used in recent years as a large-sized touch sensor such as an input/output device provided on a front surface such as a display element. The progress is constantly improving. Among the detecting electrodes, the wiring electrodes, and the connecting electrodes included in the touch sensor (panel), especially if the detecting electrodes are large in size, the resistance component is increased, so that a lower resistance electrode is required.

Conventionally, the electrode for a touch panel has a highly transparent conductive metal oxide such as an oxide semiconductor containing In, Zn, Sn, or Ti as a main component, thereby ensuring visibility of display. However, a conductive metal oxide having a high transparency has a limit in reducing the resistance value, and it is difficult to achieve a low resistance which is required in recent years. Therefore, as a substitute material, a practical use of a low-resistance metal which can ensure visibility by micro patterning is required.

Further, in an electronic device such as a touch panel in which a substrate on which an electrode is attached is disposed on the front surface of the display element, since visibility is not hindered from display, shielding or scattering, stray light, reflection, and the like are required to be as small as possible for the electrode.

However, if only a conventional electrode made of a conductive metal oxide is simply replaced with a metal, glare is generated due to the high reflectance peculiar to the metal, so it is necessary to lower the reflectance. Further, it is important to constitute an electric conductor having a low electrical resistance and being electrically connectable.

The metal having a low reflectance is molybdenum (Mo), chromium (Cr), titanium (Ti), tantalum (Ta), tungsten (W) or an alloy thereof, but these metals are of a type having a high resistance value. On the other hand, silver (Ag), aluminum (Al), copper (Cu), or the like, or an alloy thereof has a low electric resistance value, but has a high reflectance.

A method of using a metal having a high resistance value and a low reflectance to a metal having a high resistivity and a low reflectance is proposed. However, there is a limit to lowering the reflectance by a metal laminate.

Further, even if the reflectance is lowered to some extent by the metal layer, the etching rates of the respective metals are different, and therefore it is difficult to finely process each layer at a time particularly in the wet etching step. Moreover, if adjustment is performed so that a wet etching process can be performed favorably, it is difficult to fully reduce a reflectance.

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

In other words, Patent Document 1 discloses a transparent conductive film in which a blackened layer made of copper nitride and oxygen is formed on a substrate as an electromagnetic shielding film functional film for a plasma display. The visibility of the display disposed under the touch panel is not reduced by the metallic luster of the wiring portion.

Patent Document 2 discloses a film-shaped touch panel sensor that suppresses reflection from wiring by forming a black copper oxide film on the viewing side of a stripe or grid-like copper wiring provided on the film. .

Patent Document 3 discloses a touch panel sensor which is formed of an inorganic oxide material by forming a sensor electrode made of a metal material on an insulating substrate and an electrode formed on the sensor electrode. The absorbing layer, which is also an adhesive layer, can be etched with high precision and has low resistance.

Patent Document 4 discloses that a laminate of a dielectric material, a metal, a metal alloy, a metal oxide, a metal nitride, a metal oxynitride, and a metal carbide is formed on a transparent substrate. An absorption layer as a blackening layer composed of one or more types of the group, and a conductive layer containing at least one selected from the group consisting of Ni, Mo, Ti, Cr, Al, Cu, Fe, Co, V, Au, and Ag, and Improve the visibility of the conductive layer and the reflection characteristics for external light.

Further, Patent Document 5 discloses that a blackened layer made of copper, nickel, and oxygen is provided on the transparent resin substrate side of the conductor layer made of a copper plating layer, and Patent Document 6 discloses that black is provided in order. The chemical layer, the metal layer, the substrate, the blackening layer, and the metal layer, and the blackening layer is formed of copper nitride, and the visibility of the display due to the metallic gloss reflected light is suppressed from being lowered, and Patent Document 7 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, a high refractive index transparent film, a transparent conductive film, a functional transparent layer, a metal oxide, a metal nitride, a metal oxynitride, and a dielectric are disclosed as a material for forming an absorption layer. Substance and so on.

According to the methods of Patent Documents 1 to 7, etc., the reflectance caused by the metal can be absorbed by using the blackening layer or the absorbing layer, and the multilayer can be overlaid to further reduce the reflectance.

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2013-169712

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-206315

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2013-149196

[Patent Document 4] Japanese Patent Publication No. 2013-540331

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-311565

[Patent Document 6] Japanese Laid-Open Patent Publication No. 2013-129183

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2007-308761

However, the materials used in the absorption layer or the blackening layer of Patent Documents 1 to 7 have a refractive index (n) of about 1.4 to 2.5 in the visible light range, and an extinction coefficient (k) of 0.01 to 0.25, so that the absorption layer or blackening The layer is a transparent film or layer that absorbs less.

Therefore, even if the absorption layer or the 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 light range, the maximum value of the reflectance in the visible light range due to the interference of light is generated. The interference color is generated at a minimum value, and the effect of reducing the reflectance to the extent expected is not obtained.

Further, in Patent Documents 1 to 7, since the layers are repeatedly laminated, the difference in the etching rate of each layer is increased, and the selected substance is restricted.

Since the absorption layer or the blackening layer of Patent Documents 1 to 7 is a metal compound film, there is a phenomenon that in the patterning step, the metal layer cannot be etched once, and an etchant different from the metal layer is required, or even if it can be etched It is also impossible to integrate the etching rate of the metal layer and the metal compound layer, and any one of the layers formed by the laminate may be overetched or etched insufficiently, and a fine pattern cannot be formed as expected.

Further, in addition to the use of a transparent conductive film as a transparent oxide semiconductor material In the case of a metal compound as an absorbing layer or a blackening layer, depending on the presence or absence of conductivity of the absorbing layer or the blackening layer, there is a need to add a step to the connection with other connecting electrodes, or to change the composition of the film. In the case, when used as an electrode, a limitation is imposed.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a laminate having a glare (reflectance) which is reduced by the gloss of a metal, a method for producing the same, and an electronic device.

Another object of the present invention is to provide a laminate, a method for producing the same, and an electronic device which can be visually blackened by reducing the reflectance of a metal in the visible light range to a flat reflectance with a small number of layers. The color tone may be formed into a fine pattern once by wet etching in a state where the laminate is layered, and an optimum absorption layer having conductivity corresponding to a metal layer having low resistance may be provided.

The above problem can be solved by the laminated body of the present invention. The laminated body of the present invention comprises 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 in contact with the surface. The metal layer is composed of a metal layer having at least one layer of a specific resistance of 1.0 μΩ·cm to 10 μΩ·cm or a metal containing the metal as a main component, and a specific resistance of 10 μΩ·cm or less. The mixture is composed of a mixture of a transparent oxide semiconductor material and at least one metal having a free energy of formation of an oxide equal to or higher than zinc (Zn).

Since it is configured in this manner, the conductive transparent oxide semiconductor material can be arbitrarily combined with a metal having an oxide formation free energy equal to or higher than zinc (Zn), and electrical properties (electric conductivity) and optical properties can be obtained ( The refractive index and the extinction coefficient, and the etching characteristics (solubility in the etchant, etching rate) are freely controlled so as to have a desired value.

Therefore, it is possible to achieve a conductive laminated body by using a small number of layers: it is easy to electrically connect the wiring to other metal wirings, and to ensure good electrical conductivity, and at the same time, it can be suppressed by reducing the reflectance of the metal surface of the self-viewing side and blackening. Due to the glare generated by the metal layer, any fine pattern can be formed by wet etching once.

When the laminate of the present invention is used for an electrode material for an electronic device, the response speed can be improved, and the visibility can be improved by microfabrication and reflectance reduction, and the pattern can be formed by one etching, and the minimum layer composition can be borrowed. This can improve productivity and reduce costs.

Further, since the metal compound layer is composed of a mixture, the mixture is composed of a mixture of a transparent oxide semiconductor material and a metal having a free energy of oxide formation equivalent to or higher than zinc (Zn), so that conductivity is ensured, and an optical constant can be obtained ( The design of the laminated body is facilitated by the appropriateness of the refractive index, the extinction coefficient, and the absorption. Further, a laminate having a light absorbing layer having good conductivity can be obtained.

Further, since it is made of a compound which is composed only of a metal oxide, a metal nitride, a metal oxynitride, or a metal carbide, it has a large absorption layer, so that the reflectance of the surface of the metal layer can be greatly reduced. When the two layers of the metal layer and the one metal compound layer are formed, the glare of the laminate is also lowered, and when the laminate of the present invention is used for a display or the like, the visibility is improved.

Since the visibility is improved, the laminate of the present invention can be preferably used for displays such as display devices, touch panels, and the like which are required to have a beautiful appearance, and can be used for display devices, light-emitting elements, and touch panels. Electrodes for solar cells, other electronic devices, etc.

Further, the metal layer is a layer having 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·cm. In the case of using a metal layer having a low resistance in the metal layer, when the wiring pattern is formed from the metal layer and the metal compound layer, the wiring pattern can be made thinner, so that the touch panel is used for the surface of the display. It can also maintain visibility.

In the wet etching process of the present invention, the metal layer and the metal compound layer, the metal compound layer, the metal layer and the metal compound layer can be patterned once, and a fine pattern of 4 μm can be realized. Therefore, it functions as a main electrode or an auxiliary electrode of a touch panel, a display element, a light-emitting element, a photoelectric conversion element, and the like, and a connection electrode with a terminal.

A metal having an oxide generation free energy equal to or higher than zinc (Zn) is a metal which ensures conductivity and is not easily oxidized. Therefore, by mixing a metal having a free energy of oxide formation equivalent to or higher than zinc (Zn) in the metal compound layer, it is possible to effectively utilize the absorption property of the metal which is not easily oxidized.

Moreover, not only the metal layer but also the metal compound layer is electrically conductive, so that it can be electrically connected to other wirings easily, and the wiring pattern can be formed by the metal layer and the metal compound layer of the present invention.

In this case, the metal layer may be formed by laminating at least one layer of the above-mentioned alloy and a different kind of metal composed of a metal different from the metal species which is a main component of the layer of the alloy.

Since it is configured in this manner, it is easy to adjust characteristics such as optical constants and etching rates of the laminated body.

In this case, the metal layer may be composed of two or three layers, and the two or three layers may be a single layer composed of copper (Cu), aluminum (Al), silver (Ag) or an alloy of the metals. And a layer selected from the group consisting of a molybdenum (Mo) layer, a molybdenum alloy layer, an aluminum (Al) layer, and an aluminum alloy layer.

Since it is configured in this manner, the metal layer can be made low-resistance, and when the wiring pattern is formed by the metal layer and the metal compound layer, the wiring pattern can be made thinner, so that even for the display table The touch panel and the like can also maintain visibility.

In this case, the refractive index (n) of the metal compound layer in the visible light range (400 to 700 nm) may be 2.0 to 2.8, and the extinction coefficient (k) may be 0.6 to 1.6.

Since it is configured in this manner, it is possible to constitute a laminated body which suppresses reflection and has no dark black such as red, yellow or blue.

In this case, the metal compound layer may be composed of indium oxide (In ₂ O ₃ ), zinc oxide (ZnO) or tin dioxide (SnO ₂ ), or indium oxide (In ₂ O ₃ ), oxidation. One or two kinds of transparent oxide semiconductor materials containing zinc (ZnO) or tin dioxide (SnO ₂ ) as a main component, and a mixture of metals having free energy of oxide formation equivalent to or higher than zinc (Zn) Layer.

Since it is configured in this manner, it is possible to form an average reflectance in the visible light range and a small difference between the maximum reflectance and the minimum reflectance, and there is no dark black laminated body such as red, yellow or blue.

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

In this case, the metal having the oxide formation free energy equal to or higher than zinc (Zn) may be selected from the group consisting of zinc (Zn), copper (Cu), nickel (Ni), molybdenum (Mo), and cobalt (Co). Any one or more of a group of lead (Pb) and molybdenum alloy.

As described above, by adding such metals to the metal compound layer which ensure conductivity and are not easily oxidized, the absorption of the metal compound layer can be increased, and the reflectance of the laminate can be reduced.

In this case, the metal compound layer may be in a volume ratio of 8:2 to 5 by the transparent oxide semiconductor material and a metal having a free energy equivalent to that of zinc (Zn): 5 mixed.

Since it is configured in this manner, it is possible to ensure conductivity and to optimize the optical constants (refractive index, extinction coefficient, and absorption), and to form an average reflectance in the visible light range and a difference between the maximum reflectance and the minimum reflectance. Small, no dark, black, blue, etc.

In this case, the metal compound layer may contain one or more 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.

Since it is configured in this manner, the optical constant (refractive index, extinction coefficient, and absorption) of the metal compound layer constituting the laminate can be appropriately controlled by adjusting the amounts of nitrogen, oxygen, or carbon in the metal compound layer. Further, since nitrogen, oxygen or carbon in the metal compound layer has both an adjustment function of conductivity and etching characteristics (etching rate), it can be adjusted to an electrical, optical, and chemical film quality. Further, depending on the reactive gas contained, a wide range of adjustable etching characteristics and optical characteristics can be used, and a wider variety of metals or transparent oxide semiconductor materials can be used for the metal compound layer. Further, the laminate of the metal compound layer and the metal layer can be made into a fine pattern.

Further, when a metal compound layer is formed on the surface of the metal layer opposite to the substrate, the surface of the layered body is covered with a conductive material made of a nitride, an oxide or a carbide of a metal, so that it can be made. A laminate with excellent environmental resistance.

Further, a transparent oxide semiconductor material having conductivity, a metal having free energy for forming an oxide equal to or higher than zinc (Zn), and at least one of oxygen (O), nitrogen (N), and carbon (C) can be used. Arbitrarily combined, the electrical properties (conductivity), optical properties (refractive index and extinction coefficient), etching characteristics (solubility in the etchant, and etching rate) can be freely controlled so as to have desired values.

Therefore, it is possible to ensure a conductive laminated body by using a small number of layers: easy electrical wiring is connected to other metal wirings, ensuring good electrical conductivity, and by reducing the reflectance of the metal surface from the viewing side (low reflectance, And blackening) to suppress glare, and further, an arbitrary fine pattern can be formed by wet etching once.

When the laminate of the present invention is used for an electrode material for an electronic device, the response speed can be improved, and the visibility can be improved by microfabrication and reduction of reflectance, and the pattern can be formed by one etching, and the layer composition is minimized. It is possible to improve productivity and reduce costs.

In this case, in the visible light range (400 to 700 nm), the reflectance of the laminated body on the side of the metal compound layer side is 1.0% or more and 15% or less on average, and the difference between the maximum reflectance and the minimum reflectance is 10 Below %, the visual appearance is dark.

According to this configuration, the glare of the laminated body is lowered, and the visibility of the laminated body of the present invention is improved when it is used for a display or the like.

Since the visibility is improved, the laminate of the present invention can be preferably used for displays such as display devices, touch panels, and the like which are required to have a beautiful appearance, and can be used for display devices, light-emitting elements, and touch panels. Electrodes for solar cells, other electronic devices, etc.

In order to further make the laminated body dark black, it is important to select a substance whose difference between the maximum reflectance and the minimum reflectance is as small as possible. In the present invention, the difference between the maximum reflectance and the minimum reflectance is 10% or less. Therefore, a good dark black layer body can be obtained.

In this case, the laminate of the present invention may be provided, and the metal layer and the metal compound layer formed on at least one surface of the metal layer in contact with the surface may be formed on at least a part of the substrate or patterned. And formed.

Since it is constituted in this manner, the laminate of the present invention can be preferably used for various display elements. A display such as a touch panel that requires a beautiful appearance can be used as an electrode for a display device, a light-emitting element, a touch panel, a solar cell, or another electronic device.

The above problem can be solved by the method for producing a laminate according to the present invention. The method for producing a laminate according to the present invention comprises the steps of: forming a metal layer: forming at least one layer of a specific resistance of 1.0 μΩ·cm to 10 μΩ·cm on a transparent substrate. a metal layer or a layer of an alloy containing the metal as a main component to form a metal layer having a specific resistance of 10 μΩ·‧ cm or less; and a metal compound layer forming step of: at least one of before and after the metal layer forming step is made transparent The oxide semiconductor material is formed into a film with a mixture of at least one or more metals having an oxide formation free energy equal to or higher than zinc (Zn) to form a conductive metal compound layer as a light absorbing layer.

The metal compound layer is composed of a mixture of a transparent oxide semiconductor material and a metal having a free energy of oxide formation equivalent to or higher than zinc (Zn), thereby ensuring conductivity and achieving optical constant (refractive index, extinction) The appropriateness of the coefficient and absorption) makes it easy to design the laminate.

Moreover, compared with a case where only a metal oxide, a metal nitride, a metal oxynitride, or a metal carbide is used, it is a layer which absorbs a large layer, and the reflectance of the surface of a metal layer can be drastically reduced, even if it is set. In the case of a two-layer structure composed of only a metal layer and a single metal compound layer, the glare of the laminate is also lowered, and the visibility of the laminate of the present invention is improved when used in a display or the like.

Since the visibility is improved, the laminate of the present invention can be preferably used for displays such as display devices, touch panels, and the like which are required to have a beautiful appearance, and can be used for display devices, light-emitting elements, and touch panels. Electrodes for solar cells, other electronic devices, etc.

Further, the metal layer is provided with at least one layer of specific resistance of 1.0 μΩ ‧ cm to 10 A metal layer of μΩ·cm or a layer of an alloy containing the metal as a main component is composed of a metal layer having a specific resistance of 10 μΩ··cm or less. Since a metal having a low resistance is used for the metal layer, a wiring pattern is formed from the metal layer and the metal compound layer. In this case, the wiring pattern can be made thinner, so that the touch panel or the like used for the surface of the display can maintain visibility.

According to the present invention, a conductive transparent oxide semiconductor material and at least one metal having at least one oxide free energy equivalent to zinc (Zn) can be arbitrarily combined, and electrical properties (electric conductivity) and optical properties can be obtained ( The refractive index and the extinction coefficient, and the etching characteristics (solubility in the etchant, etching rate) are freely controlled so as to have a desired value.

Therefore, it is possible to achieve the following conductive laminated body by using a small number of layers, which is easy to be electrically connected to other metal wirings, and to ensure good electrical conductivity, and can be suppressed by reducing the reflectance of the metal surface from the viewing side and blackening. Due to the glare generated by the metal layer, any fine pattern can be formed by wet etching once.

When the laminate of the present invention is used for an electrode material for an electronic device, the response speed can be improved, and the visibility can be improved by microfabrication and reflectance reduction, and the pattern can be formed by one etching, and the minimum layer can be formed. Seeking improvement in productivity and cost reduction.

1‧‧ ‧ laminated body

20‧‧‧metal layer

30a, 30b‧‧‧ metal compound layer

Fig. 1 is a schematic cross-sectional view showing a laminated body 1 according to an embodiment of the present invention.

Fig. 2 is a graph showing measured values of the refractive index of a substrate on which a metal compound layer is formed at 400 to 700 nm in Examples 1 to 4 in which the ratio of ZnO to Cu is changed to form a film metal compound layer.

Fig. 3 is a graph showing the calculated values of the extinction coefficient of the substrate with the metal compound layer of Examples 1 to 4 in which the ratio of ZnO to Cu was changed to form a film metal compound layer.

Fig. 4 is a graph showing measured values of the reflectances of the laminates of Examples 1 to 4 in which a metal layer composed of Cu was formed by changing the ratio of ZnO to Cu to form a film metal compound layer.

5 is a graph showing the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminates of Examples 1 to 4 in which a metal layer composed of Cu is formed by changing the ratio of ZnO to Cu to form a film metal compound layer. Figure.

Fig. 6 is a view showing the refractive index of the substrate with the metal compound layer of Examples 5 to 14 in which the amount of nitrogen or oxygen introduced is changed to form a film Zn-Cu (5:5) metal compound layer.

Fig. 7 is a view showing the extinction coefficient of the substrate with the metal compound layer of Examples 5 to 14 in which the amount of nitrogen or oxygen introduced is changed to form a film Zn-Cu (5:5) metal compound layer.

Figure 8 is a graph showing the measured values of the reflectance of the laminates of Examples 5 to 14 in which a metal layer composed of Cu is formed by changing the amount of nitrogen or oxygen introduced into a film of a Zn-Cu (5:5) metal compound layer. Figure.

Fig. 9 is a view showing the average reflectance and maximum reflection of the laminates of Examples 5 to 14 in which a metal layer composed of Cu is formed by changing a nitrogen or oxygen introduction amount to form a Zn-Cu (5:5) metal compound layer. A plot of the difference between the rate and the minimum reflectance.

Fig. 10 is a graph showing measured values of the reflectances of the laminates of Examples 15 to 19 in which a metal layer composed of Cu was formed by changing the ratio of In ₂ O ₃ to Mo to form a film metal compound layer.

Figure 11 is a graph showing the average reflectance and maximum reflectance and minimum reflectance of the laminates of Examples 15 to 19 in which a metal layer composed of Cu is formed by changing the ratio of In ₂ O ₃ to Mo to form a film metal compound layer. The difference between the maps.

Fig. 12 is a graph showing measured values of the reflectances of the laminates of Examples 21 to 25 in which a metal layer composed of Cu was formed by changing the ratio of ZnO-Cu to In ₂ O ₃ to form a film metal compound layer.

Fig. 13 is a view showing the average reflectance and the maximum reflectance and the minimum reflectance of the laminates of Examples 21 to 25 in which a metal layer composed of Cu is formed by changing the ratio of ZnO-Cu to In ₂ O ₃ to form a film metal compound layer. A graph of the difference in reflectance.

Fig. 14 is a graph showing measured values of reflectances of the laminates of Examples 26 to 30 in which a metal layer composed of Cu was formed by changing the ratio of ZnO-Cu to SnO ₂ to form a film metal compound layer.

Figure 15 is a graph showing the average reflectance and maximum reflectance and minimum reflectance of the laminates of Examples 26 to 30 in which a metal layer composed of Cu is formed by changing the ratio of ZnO-Cu to SnO _{2 to form a} metal compound layer. The difference between the maps.

Fig. 16 is a graph showing measured values of the reflectances of the laminates of Examples 31 to 36 in which a metal layer of ZnO-Cu and SnO ₂ was formed by changing the amount of introduction of nitrogen into a metal layer of Cu.

Fig. 17 is a view showing the average reflectance and the maximum reflectance and the minimum reflectance of the laminates of Examples 31 to 36 in which a metal layer composed of Cu is formed by changing the amount of introduction of nitrogen into a metal compound layer of ZnO-Cu and SnO ₂ . A graph of the difference in reflectance.

Figure 18 is a graph showing the measured values of the reflectance of the laminates of Examples 37 to 41 in which the metal layer of the two layers of the MoNb film and the AlNd film were formed by changing the amount of introduction of nitrogen into a metal compound layer of ZnO and Cu. Figure.

Fig. 19 is a view showing the average reflectance and maximum reflection of the laminates of Examples 37 to 41 in which a metal layer composed of two layers of a MoNb film and an AlNd film is formed by changing a nitrogen gas introduction amount to form a metal compound layer of ZnO and Cu. A plot of the difference between the rate and the minimum reflectance.

Figure 20 is a graph showing the measured values of reflectance of the laminates of Examples 42 to 47 in which a metal layer composed of an AlNd film or an APC film is formed by changing a film thickness to form a metal compound layer of ZnO and Cu. Figure.

Fig. 21 is a view showing the average reflectance and the maximum reflectance and the minimum reflectance of the laminates of Examples 42 to 47 in which a metal layer composed of an AlNd film or an APC film is formed by changing a film thickness to form a metal compound layer of ZnO and Cu. A graph of the difference in reflectance.

Fig. 22 shows a metal compound layer in which two kinds of metals (Ni: Cu = 1:1) having a plasma formation free energy equal to or higher than that of Zn are formed, and a metal compound layer having a ZnO ratio of 1 to 5 is changed to Cu The average reflectance of the laminates of Examples 54 to 58 of the film and the difference between the maximum reflectance and the minimum reflectance.

Fig. 23 is a view showing the average reflectance and the maximum reflectance and the minimum reflectance of the laminates of Examples 54, 59, and 60 in which the oxygen flow rate at the time of film formation of the metal compound layer of Ni:Cu:ZnO = 1:1:1 was changed. A graph of the difference in reflectance.

Fig. 24 is a view showing measured values of the reflectance of the laminated body in the examples 54 to 60 of Figs. 22 and 23;

Fig. 25 shows that the ratio of one metal (Mo) to oxide (ZnO + Al ₂ O ₃ ) is 1:2, and the ratio of ZnO to Al ₂ O ₃ is changed to (5:1), (4.5:1.5). (4:2) A graph showing the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminates of Examples 61 to 63 in which a 50 nm metal compound layer was formed.

Fig. 26 shows that the ratio of one metal (Mo) to oxide (ZnO + Al ₂ O ₃ ) is 1:2, and the ratio of ZnO to Al ₂ O ₃ is changed to (5:1), (4.5:1.5). (4:2) A graph showing the measured values of the reflectance of the laminates of Examples 61 to 63 in which a 50 nm metal compound layer was formed.

Fig. 27 shows an embodiment 64 in which a metal layer composed of Cu or Al is formed by forming a metal compound layer (50 nm) at a ratio of ZnO:1 metal (Mo):Al ₂ O ₃ of 4.5:3:1.5. The average reflectance of the 65-layer laminate and the plot of the difference between the maximum reflectance and the minimum reflectance.

Fig. 28 shows an embodiment 64 in which a metal layer composed of Cu or Al is formed by forming a metal compound layer (50 nm) at a ratio of ZnO:1 metal (Mo):Al ₂ O ₃ of 4.5:3:1.5. A graph of the measured values of the reflectance of the 65-layer laminate.

29 is a film formation of a metal compound layer (alternating from 5 nm to 40 nm between 5 nm and 60 nm) in a ratio of ZnO:1 metal (Mo):Al ₂ O ₃ of 4.5:3:1.5, and the film formation is composed of an AlNd alloy. The metal layer (100 nm) is a graph of the average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminates of Examples 66 to 70 of the metal layer.

Fig. 30 is a view showing a film formation of a metal compound layer (each 5 nm between 40 nm and 60 nm) in a ratio of ZnO:1 metal (Mo):Al ₂ O ₃ of 4.5:3:1.5, and the film formation is composed of an AlNd alloy. A graph of the measured value of the reflectance of the layered bodies of Examples 66 to 70 of the metal layer (100 nm) as the metal layer.

31 is a film metal compound layer (between 35 nm and 65 nm) in which the ratio of ZnO:Cu=1:1 to Al ₂ O ₃ is set to (ZnO:Cu):(Al ₂ O ₃ )=10:3.5. The average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminates of Examples 71 to 73 in which Cu was formed as a metal layer after every 15 nm).

32 is a film metal compound layer (between 35 nm and 65 nm) in which the ratio of ZnO:Cu=1:1 to Al ₂ O ₃ is (ZnO:Cu):(Al ₂ O ₃ )=10:3.5. A graph showing the measured value of the reflectance of the laminate of Examples 71 to 73 in which Cu was formed as a metal layer after every 15 nm).

Hereinafter, the laminated body according to an embodiment of the present invention will be described in detail using the drawings. Bright.

<Composition of laminated body 1>

The laminated body 1 of the present embodiment can be used as a touch panel of a display device such as a liquid crystal display or a plasma display device incorporated in various electronic devices such as a mobile phone, a mobile information terminal, a game machine, a ticket vending machine, an ATM device, and a car navigation system. A substrate with an electrode attached. Further, it can also be used as a main electrode or a auxiliary electrode of a display element, a light-emitting element, a photoelectric conversion element, or the like, and a connection electrode of a terminal.

As shown in FIG. 1, the laminated body 1 of this embodiment is formed by sequentially forming the metal compound layer 30a, the metal layer 20, and the metal compound layer 30b on the transparent substrate 10.

However, the laminated body 1 of the present embodiment may be configured not to have the metal compound layer 30b depending on the application. In this case, the metal layer 20 is formed on the transparent substrate 10, and a conductive metal compound layer 30a as a metal compound layer is formed between the transparent substrate 10 and the metal layer 20.

Further, the laminated body 1 of the present embodiment may be configured not to include the metal compound layer 30a, and the metal layer 20 may be directly formed on the transparent substrate 10, and the metal compound layer 30b may be formed on the metal layer 20.

The substrate 10 is a known transparent substrate and is 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 of one or more layers of a metal having a specific resistance of 1.0 μΩ·cm to 10 μΩ·cm or a layer 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 metal element such as silver (Ag), copper (Cu) or aluminum (Al) can be used. The reason is that the laminated body 1 is used as an electrode, so In addition to the case where a particularly high resistance value is used, a metal material having a low resistance value and freely patterning is preferable as the material of the metal layer 20.

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

Further, in combination with the metal compound layers 30a and 30b, in order to effectively reduce the reflectance, molybdenum (Mo), nickel (Ni) or an alloy thereof may be used as the material of the metal layer 20, but the conductivity is slightly inferior.

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

The metal layer 20 is adjusted such that the specific resistance of the entire layer is 10 μΩ··cm or less.

The metal layer 20 may be a layer composed of a metal such as Ag, Cu, or Al having a specific resistance of 1.0 μΩ·cm to 10 μΩ·cm or an alloy thereof, or a metal layer composed of a metal different from the metal species constituting the first layer. Laminated. For example, a layer composed of a metal of Ag, Cu, or Al or an alloy thereof, and a layer composed of any of Mo, a Mo alloy, Al, and an Al alloy containing a metal different from the one layer may be used. It is composed of two or more layers.

The metal compound layers 30a and 30b of the present embodiment are composed of a mixture of a transparent oxide semiconductor material and at least one metal having a free energy of formation of oxides equivalent to or higher than zinc (Zn), and are conductive light-absorbing layers.

As the transparent oxide semiconductor material, indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin dioxide (SnO ₂ ), or any one or two kinds of additives such as Sn may be used as a main component. A transparent oxide semiconductor material or a dielectric or metal oxide, metal nitride, metal oxynitride, metal carbide or the like having a refractive index (n) of 1.7 to 2.7 equivalent thereto. However, since the metal compound layers 30a and 30b require electrical conductivity, it is preferred to use a transparent oxide semiconductor material.

A metal having a free energy of oxide formation equivalent to or higher than zinc (Zn) includes copper (Cu), nickel (Ni), molybdenum (Mo), cobalt (Co), lead (Pb), etc., and may be selected from the horizontal axis. A metal which is equal to Zn or located on the upper side of Zn in an Ellingham diagram which is a general oxide which generates a free energy for a temperature and a vertical axis.

The reason why the metal mixed in the metal compound layers 30a and 30b is a metal having a free energy for generating oxides equal to or higher than zinc (Zn) is that if an oxide is used to form a metal having a lower free energy than Zn, the mixture is mixed with When a thin film is formed by a transparent oxide semiconductor material, it reacts excessively with oxygen, and functions only as a simple additive of a transparent oxide semiconductor material, and it is difficult to obtain a film having an appropriate optical constant which is largely absorbed by a target.

Moreover, the reason why the metal having the oxide formation free energy equal to or higher than zinc (Zn) is mixed with the metal compound layers 30a and 30b is as follows.

That is, the metal layer 20 is a layer mainly for ensuring conductivity, and the metal compound layers 30a and 30b are layers for reducing glare caused by gloss due to high reflectance of the metal layer 20. Therefore, the metal compound layers 30a, 30b need to moderately absorb metal reflection. When the metal compound layers 30a and 30b are formed only of a transparent oxide semiconductor material or a dielectric or various metal compounds, the absorption of these materials is small, so that the effect of reducing the reflectance cannot be sufficiently obtained. In this case, if only the single layer of the metal compound layers 30a and 30b is insufficient, it is necessary to additionally arrange a semi-transmissive layer of metal between the metal layer 20 and the metal compound layers 30a and 30b, or a semi-transmissive layer and The metal compound layer alternately overlaps the layers.

Further, the metal compound layers 30a and 30b composed only of a transparent oxide semiconductor material or a dielectric or various metal compounds are reflected only by controlling the temperature, pressure, rate, plasma or reactive gas at the time of film formation. Flatness, flatness of the spectral characteristics in the visible range, and guidance Any of the characteristics of electrical properties and etching properties cannot meet expectations, and cannot be a layer of a laminate having sufficient functions.

Therefore, in the present embodiment, a metal having a free energy of oxide formation equivalent to or higher than zinc (Zn) is mixed in the metal compound layers 30a and 30b, and the reflectance is lowered, the flatness of the spectral characteristics in the visible light range, and the conductivity are improved. Full performance can be obtained with all etchability. Therefore, a semi-transmissive layer of metal is also not required.

Further, 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 light range (400 to 700 nm), an extinction coefficient (k) of 0.30 to 2.5, and an absorption at a film thickness of 30 to 60 nm ( α) is in the range of 20 to 60%.

In order to reduce the reflectance and visually appear blackening, it is necessary to reduce the change in the spectral reflectance in the visible light range, that is, to set the vertical axis to the spectral reflectance and the horizontal axis to the visible range of the wavelength. The shape of the figure is as flat as possible, and the reflectance of the entire visible light range is lowered.

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

In addition, it is used by mixing two types of transparent oxide semiconductor materials, or by mixing two kinds of metals having free energy of oxide formation equivalent to or higher than zinc (Zn), and the combination of substances is rich, so that it can be finely Ground control of reflectivity, etchability, and electrical conductivity.

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

By selecting the combination of the optical constant and the film thickness, the reflectance of the light incident on the side of the metal compound layers 30a and 30b of the laminated body 1 can be set to be 1.0% or more and 15% or less in the visible light range, and the maximum reflection can be formed. The difference between the ratio and the minimum reflectance was set to 10% or less, and the laminated body 1 of the dark color was visually observed.

<Method of Manufacturing Laminate 1>

The layered body 1 of the present embodiment is produced by performing a metal layer forming step of forming at least one layer of a metal having a specific resistance of 1.0 μΩ·cm to 10 μΩ·cm on the transparent substrate 10 or mainly using the metal. a layer of an alloy of the composition, forming a metal layer 20 having a specific resistance of 10 μΩ·‧ cm or less; and a metal compound layer forming step of at least one of before and after the step of forming the metal layer, the transparent oxide semiconductor material and at least One or more kinds of a mixture of metals having a free energy of oxide formation equivalent to or higher than zinc (Zn) are formed into a film to form conductive metal compound layers 30a and 30b as light absorbing layers.

Hereinafter, a method of manufacturing the laminated body 1 of the present embodiment will be described.

First, a metal compound layer forming step of forming a metal compound layer 30a composed of a mixture of a transparent oxide semiconductor material and a metal having a free energy of formation of oxides equivalent to or higher than zinc (Zn) is carried out. Conductive light absorbing layer.

In this step, a target to which a transparent oxide semiconductor material is bonded, a target to which a metal having a free energy of oxide formation equivalent to or higher than zinc (Zn) is bonded, and a transparent substrate 10 are provided in a sputtering apparatus to transparently oxidize The ratio of the volume ratio of the semiconductor material to the film of the metal having the free energy of oxide formation equal to or higher than zinc (Zn) is in the range of 8:2 to 5:5, and the bonding is performed. The target electric power of a target having a transparent oxide semiconductor material and a target having a metal having a free energy of oxide formation equivalent to or higher than zinc (Zn) is bonded, and the metal compound layer 30a is formed by sputtering.

Further, at this time, it is possible to perform sputtering using a single target in which a transparent oxide semiconductor material and a metal having a free energy of formation of an oxide equal to or higher than zinc (Zn) are mixed at a volume ratio of 8:2 to 5:5. a transparent oxide semiconductor material and a target having a volume ratio of 8:2 to 5:5 of a metal having an oxide generating energy equivalent to or higher than zinc (Zn) and other transparent oxide semiconductor materials and/or A target having a metal having free energy of oxide formation equivalent to or higher than zinc (Zn) is subjected to dual source film formation.

Then, a metal layer forming step is performed to form at least one layer of a metal having a specific resistance of 1.0 μΩ·cm to 10 μΩ·cm or a layer of an alloy containing the metal as a main component to form a metal layer having a specific resistance of 10 μΩ··cm or less. .

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 into a film by sputtering by a known method so as to have a film thickness of about 120 nm. Further, 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 may be sputter-deposited by a known method, and then a specific resistance of 1.0 μΩ·cm to 10 μΩ·cm may be employed. The other metal or an alloy containing the other metal as a main component is sputtered by a known method to thereby form a metal layer 20 composed of two layers. Further, it is also possible to form a multilayer film of three or more layers.

Then, a metal compound layer forming step of forming the metal compound layer 30b is carried out, and the metal compound layer 30b is composed of a mixture of a transparent oxide semiconductor material and a metal having a free energy of formation of oxides equivalent to or higher than zinc (Zn). Conductive light absorbing layer.

This step is carried out by a procedure for forming a metal compound layer forming step of the metal compound layer 30a.

The formation of the laminated body 1 of the present embodiment is completed by the above procedure.

Further, in the present embodiment, the metal compound layer forming step of forming the metal compound layer 30a, the metal layer forming step, and the metal compound layer forming step of forming the metal compound layer 30b are sequentially performed, but the metal compound layer is not limited thereto. The layer forming step may also be performed by only one of them.

[Examples]

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

(Test Example 1 Study of Ratio of Transparent Oxide Semiconductor Substance to Metal in Metal Compounds)

In the test example, the metal compound layer 30a composed of zinc oxide (ZnO) and copper (Cu) and the metal layer 20 made of Cu are formed on the transparent substrate 10 made of a glass substrate in the metal compound layer 30a. The ratio of ZnO to Cu was changed in four steps of 8:2, 7:3, 6:4, and 5:5, and the optical properties of the obtained laminates 1 to 4 were examined.

First, on a transparent substrate 10 made of a transparent glass substrate, a target of ZnO, which is a commercially available transparent oxide semiconductor material containing ZnO as a main component, and a Cu which is a metal having a high free energy of oxide formation are bonded. The target is placed in a sputtering apparatus, and ZnO:Cu (volume ratio) is 8:2 (Example 1), 7:3 (Example 2), 6:4 (Example 3), 5:5 (Example) 4) The method of changing the input power to perform dual-source film formation, and the metal compound layer 30a of Examples 1 to 4 was produced.

The sputtering conditions are no heating, reaching pressure 5.00E-4Pa, sputtering pressure 4.40E-1Pa, and argon atmosphere. For DC input power, ZnO target is 1.66~0.75kw, Cu target is 0.11~0.2kw, with film The thickness of 40 nm is the target film-forming metal compound layer 30a.

The film thickness of the film-forming metal compound layer 30a is from 37.2 to 44.7 nm.

The specific resistance is calculated from the measured values of the film thickness and the sheet resistance value, and the refractive index (n) and extinction coefficient (k) of the metal compound layer are calculated based on the measured values of the film thickness, the transmittance, the reflectance, and the refractive index of the substrate. ).

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

According to Fig. 2 and Fig. 3, the specific resistance is 7.32E-2~4.58E+0Ω‧cm, the refractive index is 2.17~2.7 in the visible range (400nm~700nm), and the extinction coefficient is 0.475~1.53.

Next, on the film of each of the metal compound layers 30a of Examples 1 to 4, Cu was formed by a DC sputtering method to form a film of 120 nm, and the reflectance from the back side (glass side) was measured to calculate the visible light range (400 nm to 700 nm). The difference between the average reflectance, the maximum reflectance, and the minimum reflectance. Further, when the average reflectance and the difference between the maximum reflectance and the minimum reflectance are calculated, the reflectance value cancels the reflectance of the glass surface as the light incident surface.

The results are shown in Fig. 4 and Fig. 5.

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

In Example 1, the reflectance at 700 nm was high because the film thickness of the metal compound layer was thin, and the refractive index was lower than that of the other Examples 2 to 4, and the extinction coefficient was small.

Further, in Example 1, by calculating the refractive index and the extinction coefficient, it was confirmed that the film thickness was changed to 50 nm, the maximum reflectance was 8.33%, the average reflectance was 4.08%, and the maximum and minimum reflectance were obtained. The difference is 6.57%.

Regarding the optical constant, it is understood that the ratio of Cu in the metal compound layer 30a is from 20%. The more the 50% refractive index becomes higher, the extinction coefficient also tends to become higher.

Further, it is understood that the longer the wavelength of the measurement wavelength is from 400 nm to 700 nm, the higher the value of the refractive index and the extinction coefficient become. It is considered that depending on the optical constant of Cu (especially the extinction coefficient k), the reflectance of Cu is defined by the vicinity of 550 nm, the reflectance is high in the long wavelength region, and the reflectance is low in the short wavelength region.

In the first embodiment, the difference between the maximum reflectance and the minimum reflectance is as high as 24.69%, and reddish reflection can be obtained. Further, in the fourth embodiment, the ratio of Cu in the film becomes high, so the refractive index of 500 nm to 700 nm becomes high. The extinction coefficient also becomes higher. Thereby, the reflectance in the long wavelength region is high, and the reflectance in the short wavelength region is low. The results of Example 3 in which the ratio of ZnO to Cu was 7:3 and the ratio of ZnO to Cu of 6:4 were good, and it was found that the refractive index was approximately in the range of 2.17 to 2.54, and the extinction coefficient was 0.66 to 1.20.

(Test Example 2 Study of Nitrogen Dependence)

In the present example, when ZnO is used as the transparent oxide semiconductor material and the metal compound layer 30a is formed by sputtering, the influence of the amount of nitrogen introduced on the optical characteristics is examined.

A target in which the 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 was prepared in the same manner as in Example 4 of Test Example 1.

The target was used without heating, reaching a pressure of 8.00 E-4 Pa, a sputtering pressure of 1.60 E-1 Pa, an input power of DC of 0.3 kw, and a nitrogen gas flow rate of 0 sccm (Example 5) and 10 sccm (Example 6). 20sccm (Example 7), 30sccm (Example 8), 40sccm (Example 9), 50sccm (Example 10), 60sccm (Example 11), 100sccm (Example 12), with a film thickness of 40nm Membrane metal compound layer 30a.

Further, oxygen was replaced by nitrogen at a flow rate of 5 sccm (Example 13) and 10 sccm (Example) 14) Introduction, film formation in the same manner.

With respect to the metal compound layer 30a of the examples 5 to 14, the refractive index (n) and the extinction coefficient of the metal compound layer 30a were calculated in the same manner as in Test Example 1 in terms of film thickness, transmittance, reflectance, and refractive index of the substrate ( k).

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

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

Next, on the metal compound layer 30a of Examples 5 to 14, Cu was formed into a 120 nm metal layer 20 by DC sputtering, and the layered bodies 1 of Examples 5 to 14 were produced. The reflectance of the laminate 1 of Examples 5 to 14 was measured from the back side (glass side), and the difference between the average reflectance, the maximum reflectance, and the minimum reflectance in the visible light range (400 nm to 700 nm) was calculated.

The measurement results of the reflectances of the laminated bodies 1 of Examples 5 to 12 are shown in Fig. 8. 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. 9.

As shown in Fig. 9, the average reflectance is 15% or less, and the difference between the maximum reflectance and the minimum reflectance is 10% or less. The nitrogen gas flow rate in Examples 6 to 12 is in the range of 10 sccm to 100 sccm, and the average reflectance is 10% or less. The difference between the maximum reflectance and the minimum reflectance was 5% or less in the range of 20 sccm to 100 sccm of the nitrogen gas flow rates of Examples 7 to 12 and the oxygen flow rate of 10 sccm in Example 14.

Further, a more excellent reflectance which exhibits an average reflectance of 10% or less and a difference between the maximum reflectance and the minimum reflectance of 2.5% or less is based on the nitrogen flow rate of Examples 8 to 11 The range of sccm~60sccm. 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 used as a reference for good reflectance because when the average reflectance is 10% or less, the reflection is sufficiently suppressed, and the maximum reflection is obtained. When the difference between the rate and the minimum reflectance is 2.5% or less, dark black without red, yellow, blue, or the like can be obtained.

Similarly, focusing on the refractive index and the extinction coefficient, it is known that 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, which is dark black at a lower reflection. In Examples 8 to 11, the refractive index was 2.25 to 2.66, and the extinction coefficient was in the range of 1.20 to 1.57.

Further, even when oxygen is introduced during sputtering, compared with the oxygen flow rate of 5 sccm of Example 13, the average reflectance is reduced from about 10% to about 4% at the oxygen flow rate of 10 sccm of Example 14, and the maximum reflectance is The difference in the minimum reflectance is also reduced from about 5% to about 3%. Therefore, it is understood that the refractive index and the extinction coefficient can be controlled by selecting the optimum amount of introduced gas, and the laminated body 1 which exhibits low reflection and exhibits dark black can be produced.

(Test Example 3: Examples of other constituent materials of metal compounds)

In this example, indium oxide (In ₂ O ₃ ) was used instead of ZnO of Test Examples 1 and 2 as a transparent oxide semiconductor material constituting the metal compound layer 30a, and Mo was used instead of Cu as a metal having a high free energy of oxide formation. .

A target in which a transparent oxide semiconductor material containing In ₂ O ₃ as a main component and a target in which Mo is bonded are respectively provided in a sputtering apparatus, and a volume ratio of both of the transparent oxide semiconductor material and Mo is 10:1. (Example 15), 10:2 (Example 16), 10:3 (Example 17), 10:4 (Example 18), 10:5 (Example 19), 10:10 (Example 20) In the manner of changing the input power, a dual source film formation was performed, and the metal compound layers 30a of Examples 15 to 19 were produced.

The sputtering conditions are such that the DC input power of the transparent oxide semiconductor material is in the range of 0.18 kw to 0.46 kw, and the DC of the Mo is not heated, the pressure reaches 8.00E-4Pa, the sputtering pressure is 1.60E-1Pa, or the Ar environment. The input electric power was set to a range of 0.1 kw to 0.45 kw, and the film formation metal compound layer 30a was sputtered by double source with a target of a film thickness of 40 nm.

Thereafter, on the film of the metal compound layer 30a of Examples 15 to 19, Cu was formed by a DC sputtering method to form a film of 120 nm, and the reflectance from the back side (glass side) was measured to calculate the visible light range (400 nm to 700 nm). The difference between the average reflectance, the maximum reflectance, and the minimum reflectance.

The measured value of the reflectance is shown in Fig. 10. The difference between the average reflectance, the maximum reflectance, and the minimum reflectance is shown in Fig. 11.

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

Regarding Examples 16 and 19 of 10:2 and 10:5, the average reflectance was as high as 17% and the difference between the maximum reflectance and the minimum reflectance was 3.71% and 4.16%, and the appearance was dark black.

(Test Example 4 Study of constituent materials of metal compound layer)

In this example, the metal compound layer 30a composed of an alloy of ZnO, Cu, and In ₂ O ₃ is changed in the ratio of ZnO and Cu to In ₂ O ₃ to form a film, and a preferable ratio is examined.

A ratio of ZnO as a transparent oxide semiconductor material to Cu as a metal having a high free energy of oxide formation is a target of a volume ratio of 5:5, and a target of In ₂ O ₃ is placed in a sputtering apparatus, and ZnO-Cu is used. The volume ratio of the mixture to In ₂ O ₃ was 10:1 (Example 21), 10:2 (Example 22), 10:3 (Example 23), 10:4 (Example 24), 10:5 ( In the manner of Example 25), the ratio of the input power was changed, and double-source film formation was performed to prepare the metal compound layer 30a of Examples 21 to 25.

The sputtering conditions are as follows: no heating, reaching pressure 8.00 E-4 Pa, sputtering pressure 1.60 E-1 Pa, argon (Ar) environment, the DC input power of the ZnO-Cu mixture target is set to 0.14kw~0.72kw In the range, the DC input power of the In ₂ O ₃ target was set to 0.1 kw, and the metal compound layer 30a was formed by double-source sputtering with a target of a film thickness of 40 nm.

Thereafter, on the film of the metal compound layer 30a of Examples 21 to 25, Cu was formed by a DC sputtering method to form a film of 120 nm, and the reflectance from the back side (glass side) was measured to calculate the visible light range (400 nm to 700 nm). The difference between the average reflectance, the maximum reflectance, and the minimum reflectance.

The measured value of the reflectance is shown in Fig. 12, and the difference between the maximum reflectance and the minimum reflectance is shown in Fig. 13.

The average reflectance is 15% or less, and the difference between the maximum reflectance and the minimum reflectance is 10% or less. Embodiment 23 of the ZnO-Cu mixed target and the In ₂ O ₃ target has a DC input power ratio of 10:3 to 5. 25. In Example 23, the average reflectance was 12.92%, and the difference between the maximum reflectance and the minimum reflectance was 6.17%. In Example 24, the average reflectance was 11.79%, and the difference between the maximum reflectance and the minimum reflectance was 5.80%. 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 the test example, as the ratio of In ₂ O ₃ increases, the difference between the average reflectance and the maximum reflectance and the minimum reflectance becomes small, and a laminate 1 having good optical properties more suitable for the purpose of the present invention can be obtained. .

(Research on the constituent materials of the metal compound layer of Test Example 5)

In the present embodiment, instead of using SnO ₂ In Test Example 4 The ₂ O _3, for a metal compound layer composed of ZnO, Cu, an alloy of SnO ₂ of 30a, and changing ZnO and Cu deposition ratio of SnO _2, on the preferred ratio of research.

The Sn ₂ target was used instead of the In ₂ O ₃ target of Test Example 4, and the volume ratio of the ZnO-Cu mixture to the SnO ₂ was 10:1 (Example 26) and 10:2 (Example 27). , 10:3 (Example 28), 10:4 (Example 29), 10:5 (Example 30), the ratio of input power was changed, and dual-source film formation was performed to prepare metal compounds of Examples 26 to 30. Layer 30a.

The sputtering condition is set as the DC input power of the ZnO-Cu mixture target is in the range of 0.15 kw to 0.75 kw, the DC input power of the SnO ₂ target is 0.1 kw, and the film thickness is 40 nm, and the metal is formed by double source sputtering. Compound layer.

Thereafter, on the film of the metal compound layer 30a of Examples 21 to 25, Cu was formed by a DC sputtering method to form a film of 120 nm, and the reflectance from the back side (glass side) was measured to calculate the visible light range (400 nm to 700 nm). The difference between the average reflectance, the maximum reflectance, and the minimum reflectance.

The measured value of the reflectance is shown in Fig. 14, and the difference between the maximum reflectance and the minimum reflectance is shown in Fig. 15.

The average reflectance is 15% or less, and the difference between the maximum reflectance and the minimum reflectance is 10% or less. Examples 28 to 30 in which the ratio of the DC input power of the ZnO-Cu mixture target to the SnO ₂ target is 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%, and in Example 29, the average reflectance was 9.94%, and the maximum reflectance and minimum were obtained. The difference in 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%.

As in the case of the target of In ₂ O ₃ of Test Example 4, the average reflectance decreased as the ratio of SnO ₂ increased, and the ratio of 10:4 in Example 29 produced the lowest value, so that the ZnO-Cu mixture and the ZnO-Cu mixture were The ratio of SnO ₂ is suitably 10:4.

(Test Example 6: Nitrogen Dependence Study in the Case of Using Two Kinds of Transparent Oxide Semiconductor Substances)

In the present example, when two kinds of ZnO and SnO ₂ are used as the transparent oxide semiconductor material and the metal compound layer 30a is formed by sputtering, the influence of the amount of nitrogen introduced on the optical characteristics is examined.

A target in which ZnO which is a transparent oxide semiconductor material, Cu which is a metal having a high free energy of oxide generation, and SnO ₂ are mixed at a volume ratio of 2:3:1 is prepared and placed in a sputtering apparatus.

The sputtering conditions were set to no heating, the pressure reached 8.00 E-4 Pa, the sputtering pressure was 1.60 E-1 Pa, the DC input power was 0.3 kw, and nitrogen gas was introduced into 0 sccm (Example 31) and 20 sccm in argon gas 120 sccm. Examples 32), 40 sccm (Example 33), 60 sccm (Example 34), 80 sccm (Example 35), and 100 sccm (Example 36) were each formed to have a film thickness of 40 nm.

Thereafter, on the metal compound layer 30a of Examples 31 to 36, Cu was formed into a 120 nm metal layer 20 by DC sputtering, and the layered bodies 1 of Examples 31 to 36 were produced. The reflectance of the laminated body 1 of Examples 31 to 36 was measured from the back side (glass side), and the difference between the average reflectance, the maximum reflectance, and the minimum reflectance in the visible light range (400 nm to 700 nm) was calculated.

The measurement results of the reflectances of the laminate 1 of Examples 31 to 36 are shown in Fig. 16, and the average inverse The difference between the luminescence rate and the maximum reflectance and the minimum reflectance is shown in Fig. 17.

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. The flow rate of the nitrogen gas in Examples 32 to 36 was 20 sccm to 100 sccm. 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%, and in Example 36 (nitrogen 100 sccm), the average reflectance was 2.54%, and the maximum reflectance was the smallest. The difference in reflectance was 6.76%. The average reflectance gradually decreases as the flow rate of nitrogen increases, and the difference between the maximum reflectance and the minimum reflectance becomes larger.

Further, in Example 31 (nitrogen 0 sccm), the reflectance at a wavelength of 550 nm or more was increased to 23% or more. The reason for this is that the characteristics of the reflectance of Cu have a large influence.

Further, since the reflectance decreases as the amount of introduction of nitrogen gas increases, it is understood that Cu is nitrided when a metal compound is formed by introducing nitrogen gas.

(Test Example 7: Study on the amount of nitrogen introduced into the metal compound layer in the case where the metal layer was composed of two layers of a MoNb film and an AlNd film)

In the case where the metal layer 20 of FIG. 1 is formed of two layers of a MoNb film and an AlNd film, the influence of the flow rate of nitrogen gas when the metal compound layer 30a is formed on the reflectance of the layered body 1 is examined.

A target in which a ratio of ZnO as a transparent oxide semiconductor material to Cu which is a metal having a high free energy of oxide formation is 5:5 by volume is provided in the sputtering apparatus.

The sputtering conditions were set to no heating, the pressure reached 8.00 E-4 Pa, the sputtering pressure was 1.60 E-1 Pa, the DC input power was 0.3 kw, and nitrogen gas was introduced into 20 sccm (Example 37) and 40 sccm in argon gas 120 sccm. Examples 38), 60 sccm (Example 39), 80 sccm (Example 40), and 100 sccm (Example 41) were each formed to have a film thickness of 40 nm.

Thereafter, 25 nm of molybdenum alloy (MoNb) was formed as the metal layer 20 on the metal compound layer 30a of Examples 37 to 41, and then the aluminum alloy (AlNd) was formed into a film of 100 nm to form a film of MoNb film and AlNd film. The two layers constitute the metal layer 20. The reflectance of the laminate 1 of Examples 37 to 41 was measured from the back side (glass side), and the difference between the average reflectance, the maximum reflectance, and the minimum reflectance in the visible light range (400 nm to 700 nm) was calculated.

The measurement results of the reflectances of the laminate 1 of Examples 37 to 41 are shown in Fig. 18. The difference between the average reflectance and the maximum reflectance and the minimum reflectance is shown in Fig. 19.

As shown in Fig. 19, the average reflectance is 15% or less, and the difference between the maximum reflectance and the minimum reflectance is 10% or less. The nitrogen flow rate in Examples 39 to 41 is 60 sccm to 100 sccm, and Example 39 (nitrogen flow rate) In 60 sccm), the average reflectance was 13.71%, and the difference between the maximum reflectance and the minimum reflectance was 5.71%. Further, 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 in average reflectance, maximum reflectance, minimum reflectance, maximum reflectance, and minimum reflectance as the flow rate of nitrogen gas at the time of formation of the metal compound layer 30a was increased from 20 sccm to 100 sccm. The values all go low, showing better optical properties. From this result, it was found that Cu was leached from the target by introducing nitrogen gas during sputtering.

Further, in the range of the flow rate of 20 sccm to 100 sccm, the reflectance continuously decreases as the flow rate of nitrogen gas increases, and the average reflectance, the maximum reflectance, the minimum reflectance, and the maximum reflectance when the nitrogen flow rate is 100 sccm as the maximum flow rate of this example. The value of the difference from the minimum reflectance is also not the lowest value. Therefore, it is understood that by further increasing the amount of introduction of nitrogen gas to 100 sccm or more, a laminated film having a better low reflectance can be obtained.

(Test Example 8 Metal in the case where the metal layer was made of an AlNd film or an APC film Study of compound film thickness)

Regarding the case where the metal layer 20 of FIG. 1 is an Al alloy (AlNd) film or an Ag alloy (APC: Ag-Pd-Cu alloy) film, the reflectance characteristics of the film thickness of the metal compound layer 30a to the laminated body 1 are investigated. The impact.

A target in which a ratio of ZnO as a transparent oxide semiconductor material to Cu which is a metal having a high free energy of oxide formation is 5:5 by volume is provided in the sputtering apparatus.

The sputtering conditions were set to be no heating, the pressure reached 8.00E-4Pa, the sputtering pressure was 1.60E-1Pa, and the DC input power was 0.3kw, and the film thickness was 40 nm in an environment of introducing 60 sccm of nitrogen gas into 120 sccm of argon gas. A ZnO-Cu film as a metal compound was formed into a film of 50 nm and 60 nm to obtain a metal compound layer 30a.

Then, on the metal compound layer 30a having a film thickness of 40 nm, 50 nm, and 60 nm, a metal layer 20 is formed by forming a film of an aluminum alloy (AlNd) of 100 nm or an Ag alloy (APC) of 100 nm as the metal layer 20, respectively.

The film thickness of the metal compound layer 30a is 40 nm, 50 nm, 60 nm, and the metal layer 20 is AlNd, respectively, in Examples 42 to 44, and the film thickness of the metal compound layer 30a is 40 nm, 50 nm, 60 nm, and the metal layer 20 is The case of APC is set to Examples 45 to 47, respectively.

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

The measurement results of the reflectances of the laminated bodies 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. 21 .

Implementation of film formation of AlNd on metal compound layer 30a having a film thickness of 40 nm In Example 42, 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 was 4.36% to 6.71%. Within the range, a layered body 1 having a visually dark color and a preferable reflectance characteristic can be obtained.

(Test Example 9 Etchability Evaluation)

In this example, the evaluation of the etching property of the laminated body 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) of Test Example 2 was carried out.

By the same conditions as in the examples 11 and 12 of the test example 2, on the substrate 10 made of a glass substrate, a target having a nitrogen gas flow rate of 60 sccm and 100 sccm was sputtered by mixing ZnO and Cu at a volume ratio of 5:5. The metal compound layer 30a having a film thickness of 40 nm was formed by plating, and the metal layer 20 made of Cu having a thickness of 120 nm was formed on the metal compound layer 30a by sputtering, and the layered bodies 1 of Examples 48 and 49 were obtained.

Further, under the same conditions as in the sixth embodiment of Test Example 2, a target having a glass substrate flow rate of 10 sccm was sputtered on a substrate 10 made of a glass substrate by sputtering a target having 5% mixed with Cu at a volume ratio of 5:5. The metal compound layer 30a having a film thickness of 40 nm was formed on the metal compound layer 30a by sputtering to form a metal layer 20 made of Cu having a film thickness of 120 nm, whereby the layered body 1 of Example 50 was obtained.

A film was formed by sputtering a target having a volume ratio of 5:5 by volume of ZnO and Cu on a substrate 10 made of a PET film under the same conditions as in Example 11 of Test Example 2 at a flow rate of nitrogen of 60 sccm. The metal compound layer 30a having a thickness of 40 nm was formed on the metal compound layer 30a by sputtering to form a metal layer 20 made of Cu having a film thickness of 120 nm, whereby the layered body 1 of Example 51 was obtained.

It was composed of a PET film by the same conditions as in Example 6 of Test Example 2. The substrate 10 was sputtered with a nitrogen gas flow rate of 60 sccm using a target in which ZnO and Cu were mixed at a volume ratio of 5:5 to form a metal compound layer 30a having a film thickness of 40 nm, and formed on the metal compound layer 30a by sputtering. The metal layer 20 made of Cu having a film thickness of 120 nm was further sputtered with a target of mixing ZnO and Cu at a volume ratio of 5:5 at a nitrogen gas flow rate of 60 sccm to form a metal compound layer 30b having a film thickness of 40 nm. 52 layer body 1.

For the laminates of Examples 48 to 52, two kinds of etching using a nitric acid-hydrogen peroxide system (Ech-1, manufactured by GEOMATEC Co., Ltd.) and a phosphoric acid-nitric acid-acetic acid system (Ech-2, manufactured by GEOMATEC Co., Ltd.) were used. The agent is etched.

The laminates 1 of Examples 48 to 52 were each cut into 50 mm × 50 mm, immersed in each etchant, and controlled so that the liquid temperature became constant, and the etching end time (end point) was confirmed.

Regarding the etching end points of Examples 48 to 50 using a glass substrate, the etchant of the nitric acid-hydrogen peroxide system (Ech-1) was 20 seconds, which was the etching of the phosphoric acid-nitric acid-acetic acid (Ech-2) at the same time. The agent is 45 to 50 seconds and requires more than twice the time of Ech-1.

Regarding the etching end points of Examples 51 and 52 using the film substrate, the etchant of the nitric acid-hydrogen peroxide system (Ech-1) was 17 to 18 seconds, and the etchant of the phosphoric acid-nitric acid-acetic acid (Ech-2) was 38. ~44 seconds, which is slightly faster than about 10% of the examples 48 to 50 using the glass substrate.

(Test Example 10 Etching Evaluation of Test Pattern)

Using the laminate 1 of Examples 48 to 52 produced in the same manner as in Test Example 9, a test pattern of 20 μm, 10 μm, and 4 μm was used for the plate, and an etchant of a nitric acid-hydrogen peroxide system (Ech-1) was used. And phosphoric acid-nitric acid-acetic acid (Ech-2), wet etching, and confirm each sample The size of the pattern.

The results are shown in Table 1.

In Table 1, the pattern width is a measurement of the width of the pattern obtained after etching, and the back width is a value obtained by dividing the average of the difference between the resist width of each resist width and the measured value of the pattern width. 2, and calculate the average value of the one-side size with respect to the resist pattern retreating.

As shown in Table 1, the etchant of the nitric acid-hydrogen peroxide system (Ech-1) has an average size of about 0.5 to 0.6 μm with respect to the resist pattern, and is retracted (overetched) to form 20 μm. 10 μm and 4 μm are basic patterns. It is a good pattern whether viewed from either the front or the back.

In the case of the etchant of the phosphoric acid-nitric acid-acetic acid (Ech-2), the 20 μm pattern was confirmed, but the pattern of 10 μm and 4 μm could not be confirmed, and the pattern of the metal layer 20 was overhanged, and the like was not obtained. The result.

However, it can be seen that any etchant can form a positive pattern by adjusting the concentration or blending ratio of the etchant.

(Test Example 11 Etching Evaluation of Test Pattern)

In this example, the etching property of the layered body 1 produced under the conditions of Example 30 (volume ratio of ZnO-Cu mixture to SnO ₂ of 10:5) of Test Example 5 was evaluated.

By the same conditions as in the example 30 of the test example 5, sputtering was performed on the substrate 10 made of a glass substrate so that the volume ratio of the ZnO-Cu mixture to the SnO ₂ was 10:5, and the film thickness was 40 nm. The metal compound layer 30a is formed on the metal compound layer 30a by sputtering to form a metal layer 20 made of Cu having a thickness of 120 nm, and further, the volume ratio of the ZnO-Cu mixture to the SnO ₂ is 10:5. The metal compound layer 30b having a film thickness of 40 nm was formed by plating, and the layered body 1 of Example 53 was obtained.

Using the layered body 1 of Example 53, an etchant of a nitric acid-hydrogen peroxide system (Ech-1) and an etchant of ferric chloride (Ech-3, manufactured by GEOMATEC Co., Ltd.) were used, and 20 μm, 10 μm, and 4 μm were used. The test pattern plate was etched and the pattern size of the sample was confirmed.

The results are shown in Table 2.

According to the results of Table 2, the etchant of the nitric acid-hydrogen peroxide system (Ech-1) has an average side size of about 0.2 μm with respect to the resist pattern, and is retreated (overetching), and etching with respect to ferric chloride. The agent (Ech-3) has a retreat of about 0.5 μm (overetching), and can form a pattern of 20 μm, 10 μm, and 4 μm. However, regarding the etchant (Ech-3) of ferric chloride, the etching rate of the metal compound layers 30a and 30b is fast, so that it is confirmed by the Cu at the end of the pattern when viewed from either the front side or the back side. Cause the reflection.

(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 30a composed of two kinds of metals of Cu and Ni and ZnO is formed, and then Cu is used as the metal layer 20. First, an alloy target of Cu and Ni (1:1) and a ZnO target are placed in the apparatus, and the output of each target is adjusted so as to be a ratio of Cu:Ni:ZnO=1:1:1 to 5. Five kinds of metal compound layers 30a having a film thickness of approximately 55 nm were formed by double source sputtering.

The sputtering conditions are no heating, reaching pressure 5.00 E-4 Pa, sputtering pressure 4.3 E-1 Pa, argon atmosphere, about DC input power, ZnO target is 1.66~0.35kw, Cu target is 0.2kw, with film The metal compound layer 30a is formed to a target of 55 nm in thickness. Next, on the metal compound layer 30a, a metal layer 20 made of Cu having a film thickness of 120 nm was formed by sputtering using another Cu target, and the laminates of Examples 54 to 58 were obtained.

Further, at a ratio of Cu:Ni:ZnO = 1:1:1, oxygen was introduced at a rate of 2 sccm and 4 sccm at the time of film formation, and the laminates of Examples 59 to 60 were obtained.

The reflectances of the laminates of Examples 54 to 60 were measured from the side of the metal compound layer 30a (glass side), and the average reflectance and maximum reflectance in the visible light range (400 nm to 700 nm) were calculated. The difference between the minimum reflectances. The average reflectance, the difference between the maximum reflectance and the minimum reflectance of the laminates of Examples 54 to 60 are shown in Fig. 22 and Fig. 23, and the measurement results of the reflectance are shown in Fig. 24.

When oxygen is not introduced during film formation, the average reflectance is 15% or less, and the difference between the maximum reflectance and the minimum reflectance is 10% or less. As shown in FIG. 23, the ratio of Cu:Ni:ZnO is 1. : Embodiments 55 to 57 of 1:2~4.

In the case where oxygen was not introduced at the time of film formation, in Example 54 of Example 1:1:1 and 1:1:5 ratio of 1:1:1, the reflectance did not reach the level of the expected reflectance of 15% or less. In Example 58 in which the ratio of oxides was 1:1:5, it was considered that the absorption of the metal compound layer was small, so that the reflectance was increased.

On the other hand, when the ratio is 1:1:1, it is understood that in the examples 59 and 60 of FIGS. 23 and 24, after the reaction gas such as oxygen O ₂ = 2 sccm or 4 sccm is introduced into the film formation, Results The average reflectance in Example 59 was 15.75%, the difference between the maximum reflectance and the minimum reflectance was as low as 5.65%, the average reflectance in Example 60 was 14.78%, and the difference between the maximum reflectance and the minimum reflectance was as low as 6.12%. , get a good reflectivity.

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

An oxide mixed target of ZnO, alumina (Al ₂ O ₃ ) and Mo (5:1:3), (4.5:1.5:3), (4:2:3) is prepared as the constituent metal compound layer 30a. Transparent oxide semiconductor material.

The oxide mixed target was placed in the apparatus, and the sputtering condition was set to be no heating, the pressure reached 8.00 E-4 Pa, the sputtering pressure was 1.60 E-1 Pa, the argon gas was 120 sccm, and the input power was 0.3 kW to form a metal compound layer. After 30a, the AlNd alloy was laminated to 120 nm to form a metal layer 20, and an example was obtained. The layered body of 61~63.

The reflectances of the laminates of Examples 61 to 63 were measured from the side of the metal compound layer 30a (glass side), and the difference between the average reflectance, the maximum reflectance, and the minimum reflectance in the visible light range (400 nm to 700 nm) was calculated. The average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminates of Examples 61 to 63 are shown in Fig. 25, and the results of measurement of the reflectance are shown in Fig. 26.

As shown in Fig. 25 and Fig. 26, in the examples 61 to 63, the average reflectance, the difference between the maximum reflectance and the minimum reflectance were both 10% or less, and a dark black film which was observed from the viewing side was obtained. The large difference caused by the ratio of ZnO to Al ₂ O _{3 was} not confirmed.

Further, Cu and Al of 50 nm were formed on the metal compound layer 30a of the ZnO, Al ₂ O ₃ and Mo ratio of Example 62 in the range of 4.5:1.5:3, and the metal layer 20 was formed into a two-layer structure. 64, 65 layer body.

In Examples 64 and 65, the average reflectance, the difference between the maximum reflectance and the minimum reflectance were both 10% or less, and in a region having a film thickness of 50 nm and a visible light range of 400 to 700 nm, it was found that compared with Cu, The case of Al film formation becomes a lower reflectance. The reason is considered to be that the peak of the lowest reflectance which is the lowest value of the reflectance is shifted due to the influence of the refractive index of Cu and Al and the extinction coefficient. In the case of forming a Cu film, the average reflectance of Example 64 and the difference between the maximum reflectance and the minimum reflectance may be lowered by reducing the film thickness of the metal compound layer 30a to 35 nm to 40 nm.

Further, in the film of the metal compound layer 30a in which the ratio of ZnO, Al ₂ O ₃ and Mo of Example 62 was 4.5:1.5:3 was between 40 nm and 60 nm, the film was formed by AlNd every 5 nm. The metal layer 20 of the alloy was obtained, and the laminates of Examples 66 to 70 were obtained.

The inverse of the laminates of Examples 66 to 70 was measured from the side of the metal compound layer 30a (glass side). The incident rate is calculated as the difference between the average reflectance, the maximum reflectance, and the minimum reflectance in the visible light range (400 nm to 700 nm). The average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminates of Examples 66 to 70 are shown in Fig. 29, and the results of measurement of the reflectance are shown in Fig. 30.

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 15% or less, which was 7.50%. In Fig. 29, of course, the film thickness dependence is clearly expressed. It can be easily predicted that this case is also suitable for the case where the metal layer 20 is set to Cu as described above.

(Test Example 14 is an example in which a metal compound layer (ZnO: Cu = 1:1) and one metal oxide)

As a transparent oxide semiconductor material constituting the metal compound layer 30a, a target of 1:1 ratio of ZnO and Cu and a target of Al ₂ O ₃ are placed in the device, and a metal compound layer 30a (ZnO: Cu = 1:1) is used. The output of each sputtering power supply is adjusted so that the ratio of one metal oxide (Al ₂ O ₃ ) is (ZnO-Cu):(Al ₂ O ₃ )=10:3.5, and the film thickness is 35 nm, 50 nm, and 65 nm. The target is formed into three metal compound layers 30a. Thereafter, Cu of 120 nm was laminated as the metal layer 20, and the laminates of Examples 71 to 73 were obtained.

The reflectances of the laminates of Examples 71 to 73 were measured from the side of the metal compound layer 30a (glass side), and the difference between the average reflectance, the maximum reflectance, and the minimum reflectance in the visible light range (400 nm to 700 nm) was calculated. The average reflectance and the difference between the maximum reflectance and the minimum reflectance of the laminates of Examples 71 to 73 are shown in Fig. 31, and the results of measurement of the reflectance are shown in Fig. 32.

In Examples 71 and 72 in which the thickness of the metal compound layer 30a was 35 or 50 nm, the average reflectance was 15% or less, and the difference between the maximum reflectance and the minimum reflectance was 10% or less. Metal compound layer In Example 73 in which the film thickness of 30a was 65 nm, the difference between the maximum reflectance and the minimum reflectance was 10% or less, 2.41%, and the average reflectance was 16.25%.

When the metal compound layer 30a is a film thickness of any of 35 nm, 50 nm, and 65 nm, a reflectance with good flatness can be obtained. In Example 73 in which the thickness of the metal compound layer 30a was 65 nm, the reflectance of the entire visible light range was high, but the difference between the maximum reflectance and the minimum reflectance was small, so that the film was darkened and the appearance was good.

In the conventional laminated body in which the layer of the transparent oxide semiconductor material is simply combined with the metal layer, the interference color due to the decrease in the reflectance and the lowest value is likely to become apparent in the relationship between the refractive index and the extinction coefficient. On the other hand, according to the above examples, it is understood that a combination of a metal compound layer composed of a mixture of a metal having a free energy of oxide formation equivalent to or higher than that of zinc oxide and a metal layer can be obtained to obtain a dark black color. Laminated film.

Claims (10)

A laminated body 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 in contact with the surface, wherein the metal layer is provided with at least One layer of a metal having a specific resistance of 1.0 μΩ·cm to 10 μΩ·cm or a layer of an alloy containing the metal as a main component is composed of a metal layer having a specific resistance of 10 μΩ··cm or less, and the metal compound layer is composed of a mixture, and the mixture is transparent. a mixture of an oxide semiconductor material and at least one metal having a free energy of formation of an oxide equal to or higher than zinc (Zn); the metal layer is composed of 2 or 3 layers, and the 2 or 3 layers are laminated: a single layer composed of (Cu), aluminum (Al), silver (Ag) or an alloy of the metals, and selected from the group consisting of a molybdenum (Mo) layer, a molybdenum alloy layer, an aluminum (Al) layer, and an aluminum alloy layer Layer. The laminate according to claim 1, wherein the metal layer is a layer of the alloy of at least one layer and a different metal layer composed of a metal different from the metal species which is a main component of the layer of the alloy. Made. The laminate of the first aspect of the patent application, wherein the metal compound layer has a refractive index (n) of 2.0 to 2.8 in the visible light range (400 to 700 nm) and an extinction coefficient (k) of 0.6 to 1.6. The laminate of claim 1 or 3, wherein the metal compound layer is composed of a layer consisting of indium oxide (In ₂ O ₃ ), zinc oxide (ZnO) or tin dioxide (SnO ₂ ), or Indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), or tin dioxide (SnO ₂ ) as a main component, containing one or two kinds of transparent oxide semiconductor materials as additives, and having the same or higher than zinc (Zn) A layer of a mixture of metals in which the oxide generates free energy. The laminate according to claim 4, wherein the metal having free energy of oxide formation equivalent to or higher than zinc (Zn) is selected from the group consisting of zinc (Zn), copper (Cu), nickel (Ni), and molybdenum ( A metal of any one or more of the group consisting of Mo), cobalt (Co), lead (Pb), and molybdenum alloy. The laminate according to claim 5, wherein the metal compound layer is a metal of the transparent oxide semiconductor material and having a free energy equivalent to that of zinc (Zn), in a volume ratio of 8:2 to 5: 5 mixed. The laminate according to claim 1 or 3, wherein 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 is The range of 30 nm to 60 nm. The laminate of the first or third aspect of the patent application, wherein in the visible light range (400 to 700 nm), the reflectance of the laminated body on the side of the metal compound layer side is 1.0% or more and 15% or less, and the maximum reflection is obtained. The difference between the rate and the minimum reflectance is 10% or less, and the visual appearance is dark. An electronic device comprising the laminate of claim 1 or 3, wherein the metal layer and the metal compound layer formed on at least one side of the metal layer in contact with the surface are formed on at least a portion of the substrate Or formed by patterning. A method for manufacturing a laminate, comprising the steps of: forming a metal layer on a transparent substrate by forming at least one layer of a metal having a specific resistance of 1.0 μΩ·cm to 10 μΩ·cm or a layer of an alloy containing the metal as a main component; Forming a metal layer having a specific resistance of 10 μΩ·‧ cm or less; and forming a metal compound layer: at least one before and after the metal layer forming step Forming a transparent oxide semiconductor material with at least one kind of a mixture of at least one metal having a free energy of formation of oxides equal to or higher than zinc (Zn) to form a metal compound layer having conductivity as a light absorbing layer; It consists of 2 layers or 3 layers, which are: a single layer composed of copper (Cu), aluminum (Al), silver (Ag) or an alloy of these metals, and selected from molybdenum (Mo a layer of a group consisting of a layer, a molybdenum alloy layer, an aluminum (Al) layer, and an aluminum alloy layer.