TW201545897A - Laminate, conductive laminate and electronic device - Google Patents

Abstract

Provided is a laminate which is capable of obtaining a crystalline indium tin oxide layer by a heat treatment, and which is capable of decreasing the visibility of an etching pattern that is formed on the indium tin oxide layer. This laminate comprises a transparent base, a foundation layer and an indium tin oxide layer. The foundation layer is laminated on the transparent base, and contains silicon, oxygen and nitrogen. The indium tin oxide layer is laminated on the foundation layer, and is mainly composed of an amorphous indium tin oxide. This laminate has a reflectance difference ([increment]R) of 1% or less after a heat treatment at a heat treatment temperature of 150 DEG C with a heat treatment duration of 30 minutes. The reflectance difference ([increment]R) is the absolute value of the difference between the average reflectance (R1) [%] of positions where the indium tin oxide layer is present and the average reflectance (R2) [%] of positions where the indium tin oxide layer is absent.

Description

Laminated body, conductive laminated body, and electronic equipment

The present invention relates to a laminate, a conductive laminate, and an electronic device.

Since the transparent conductive film has electrical conductivity and optical transparency, it is used as a transparent electrode, a dustproof film, and an electromagnetic wave shielding film. In recent years, as an electrode for a capacitive touch panel, a transparent conductive film has attracted attention. As the transparent conductive film, an indium tin oxide film can be preferably used.

In the case of an electrostatic capacitance type touch panel electrode, the indium tin oxide film is patterned by etching. Therefore, the etching property of the indium tin oxide film is required to be good. Further, in the case of the indium tin oxide film, the visibility of the etching pattern is required to be low, so that the appearance when the touch panel or the like is formed becomes good. Further, the indium tin oxide film is required to have light transmittance, conductivity, durability against mechanical contact, and the like.

As a method of producing an indium tin oxide film, a method of performing sputtering while facing a substrate is known. According to the above method, an indium tin oxide film which is excellent in crystallinity, conductivity, and durability can be produced. However, since it is crystalline, etchability does not become good.

On the other hand, as a method for producing an indium tin oxide film, a method of performing sputtering at room temperature and a method of introducing water to perform sputtering are known. According to the above method, an indium tin oxide film which is amorphous and has excellent etching properties can be produced. However, since it is amorphous, electrical conductivity and durability do not become good.

In order to solve such a problem, a method is known in which an amorphous indium tin oxide film is formed and then etched, and further heat-treated to form a crystalline indium tin oxide film. borrow According to the above method, etchability, electrical conductivity, and durability are improved. Hereinafter, such a method will be referred to as a crystallization method.

In general, as for the indium tin oxide film, as the thickness is reduced, the transmittance is increased, so that the visibility of the etching pattern is lowered. However, in the case of the crystallization method, if the thickness is reduced, crystallization by heat treatment becomes difficult, and thus conductivity and durability are not improved. The conductivity can be improved by increasing the content ratio of tin oxide in the indium tin oxide. However, if the content ratio of the tin oxide is high to some extent, crystallization due to heat treatment becomes difficult, and thus the conductivity does not necessarily become good.

Conventionally, various manufacturing methods have been proposed as a method of producing a transparent conductive film (see, for example, Patent Document 1). Further, it is known that a base layer is provided between the base material and the transparent conductive film in order to suppress peeling of the base material from the transparent conductive film (see, for example, Patent Documents 2 and 3).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-224152

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-197925

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-093318

The present invention has been made to solve the above problems, and an object of the invention is to provide a crystalline indium tin oxide layer by heat treatment, and to reduce visibility of an etching pattern formed on an indium tin oxide layer. Laminated body. Further, an object of the present invention is to provide a conductive laminated body having a crystalline indium tin oxide layer and having a low visibility of an etching pattern formed on an indium tin oxide layer. Further, it is an object of the invention to provide an electronic device having such a conductive laminate.

The laminate of the present invention has a transparent substrate, a base layer, and an indium tin oxide layer. The base layer is layered on a transparent substrate and contains cerium, oxygen, and nitrogen. The indium tin oxide layer is laminated on the underlying layer and mainly contains amorphous indium tin oxide. The laminate of the present invention is heat-treated at a heat treatment temperature of 150 ° C and a heat treatment time of 30 minutes, and the following reflectance difference ΔR is 1% or less. The reflectance difference ΔR is based on the transparent substrate side as the light incident surface, and the average reflectance R ₁ [%] at a position of the indium tin oxide layer at a wavelength of 480 nm or more and 650 nm or less, and the absence of indium tin oxidation. The absolute value of the difference between the average reflectance R ₂ [%] at a wavelength of 480 nm or more and 650 nm or less at the position of the object layer.

The conductive laminate of the present invention has a transparent substrate, a base layer, and an indium tin oxide layer. The base layer is layered on a transparent substrate and contains cerium, oxygen, and nitrogen. The indium tin oxide layer is laminated on the base layer and mainly contains crystalline indium tin oxide. The following reflectance difference ΔR of the conductive laminate of the present invention is 1% or less. The reflectance difference ΔR is based on the transparent substrate side as the light incident surface, and the average reflectance R ₁ [%] at a position of the indium tin oxide layer at a wavelength of 480 nm or more and 650 nm or less, and the absence of indium tin oxidation. absolute value at the wavelength of 480nm or more and 650nm or less of the average reflectivity R ₂ [%] of the difference between the position of the layer.

The electronic device of the present invention has the electroconductive laminate of the present invention.

In the present invention, a base layer containing ruthenium, oxygen, and nitrogen is disposed between the transparent substrate and the amorphous indium tin oxide layer. By the underlayer, crystallization of the indium tin oxide layer by heat treatment becomes good. Moreover, the visibility of the etching pattern formed on the indium tin oxide layer is also lowered by the underlying layer.

10‧‧‧Layer

11‧‧‧Transparent substrate

12‧‧‧ basal layer

13‧‧‧Amorphous indium tin oxide layer

13a‧‧‧ Part of the indium tin oxide layer 13

13b‧‧‧There is no part of the indium tin oxide layer 13

20‧‧‧Electrical laminate

21‧‧‧ crystalline indium tin oxide layer

21a‧‧‧ Part of the indium tin oxide layer 21

21b‧‧‧There is no part of the indium tin oxide layer 21

Fig. 1 is a cross-sectional view showing an example of a laminate of the present invention.

Fig. 2 is a cross-sectional view showing an example of the conductive laminate of the present invention.

Fig. 1 is a cross-sectional view showing an example of a laminate of the present invention.

The laminated body 10 has, for example, a transparent substrate 11, a base layer 12, and an amorphous indium tin oxide layer 13 in this order. Here, the indium tin oxide layer 13 is a crystalline indium tin oxide layer by heat treatment.

(transparent substrate)

The transparent substrate 11 is preferably, for example, an unstretched or stretched plastic film of a polyolefin such as polyethylene or polypropylene; polyethylene terephthalate, polybutylene terephthalate or polynaphthalene. Polyester such as ethylene diformate; polyamine which is nylon 6, nylon 66; polyimine, polyarylate, polycarbonate, polyacrylate, polyether oxime, polyfluorene; copolymers of these. Further, as the transparent substrate 11, other plastic films having a high transparency and a glass substrate can be used. The transparent substrate 11 may have a single layer structure or a laminate structure having two or more layers having different compositions. As the transparent substrate 11, a polyethylene terephthalate film is particularly preferable.

A hard coat layer, a primer layer, an undercoat layer, or the like may be provided on one surface or both surfaces of the transparent substrate 11. Here, the hard coat layer is such that the transparent substrate 11 is less likely to be damaged. The undercoat layer is used to improve the adhesion of organic materials to inorganic materials. The primer coating is a refractive index adjusting layer or the like which reduces the visibility of the etching pattern formed on the indium tin oxide layer 13. Further, the transparent substrate 11 can be subjected to surface treatment such as easy subsequent treatment, plasma treatment, or corona treatment. The thickness of the transparent substrate 11 is preferably 10 μm or more and 200 μm or less, and more preferably 25 μm or more and 180 μm or less from the viewpoints of flexibility, durability, and the like.

(base layer)

The underlayer 12 is provided to promote crystallization of the indium tin oxide layer 13. The base layer 12 is combined with a ruthenium oxide layer (SiO ₂ layer), a tantalum nitride layer (Si ₃ N ₄ layer), a magnesium fluoride layer (MgF ₂ layer), an aluminum oxide layer (Al ₂ O ₃ layer), and the like. The ratio can greatly promote crystallization. In particular, even when the thickness of the indium tin oxide layer 13 is thin, or when the ratio of tin in the indium tin oxide layer 13 is large in terms of oxide, it can be well crystallized. .

The base layer 12 contains antimony, oxygen, and nitrogen as essential components. Further, the ratio of each element can be appropriately selected depending on the effect of promoting crystallization, the required refractive index, and the like. Further, it may further contain other elements, and for example, aluminum (Al) or carbon (C) may be contained.

When the underlying layer 12 contains nitrogen, for example, the resistance to alkali (hereinafter also referred to as alkali resistance) is greatly improved as compared with the underlayer containing cerium oxide. Thereby, when the process of exposure to an alkaline chemical such as an etching process is performed, damage such as peeling and defects of the film can be suppressed. Further, the underlying layer 12 contains nitrogen, and is harder than, for example, a base layer containing cerium oxide. Thereby, the scratch resistance of the laminated body 10 is also improved.

The ratio of the number of molecules of N ₂ /O ₂ contained in the underlayer 12 is preferably 0.03 or more and 15 or less, and more preferably 0.05 or more, from the viewpoint of crystallinity and resistance value after heat treatment of the indium oxide layer 13 . Further, 10 or less is particularly preferably 0.07 or more and 5 or less. The ratio of the number of molecules can be determined by electron beam spectroscopic analysis or secondary ion mass spectrometry.

The refractive index of the underlayer 12 at a wavelength of 500 nm is preferably 1.48 or more, more preferably 1.49 or more. Further, the refractive index of the underlayer 12 at a wavelength of 500 nm is preferably 2.00 or less, more preferably 1.95 or less, still more preferably 1.9 or less. Any refractive index of the above range can be obtained by adjusting the ratio of ruthenium, oxygen, and nitrogen in the base layer 12. By adjusting the refractive index of the underlying layer 12, it is easy to adjust the refractive index of the entire constituent layer regardless of the refractive index of each layer (hereinafter also simply referred to as a constituent layer) constituting the laminated body 10 other than the underlying layer 12. When the refractive index of the underlying layer 12 is within the above range, the effect of lowering the visibility of the etching pattern formed on the indium tin oxide layer 13 is large.

The thickness of the underlayer 12 is preferably 1 nm or more. When the thickness is 1 nm or more, the effect of promoting crystallization of the indium tin oxide layer 13 is large. Further, when the thickness is 1 nm or more, the effect of lowering the visibility of the etching pattern formed on the indium tin oxide layer 13 is large. The thickness of the underlayer 12 is more preferably 3 nm or more, further preferably 5 nm or more, and particularly preferably 7 nm or more from the viewpoint of promoting the crystallization and reducing the visibility of the etching pattern. The thickness of the base layer 12 is preferably 100 nm from the viewpoint of productivity and the like. Hereinafter, it is more preferably 80 nm or less, further preferably 70 nm or less. Furthermore, the base layer 12 may have a single layer structure or a laminate structure having two or more layers having different compositions. In the case of a laminated structure, the refractive index of the underlying layer 12 may be replaced by the refractive index and thickness of the underlying film layer 12 in contact with the indium oxide layer 13 instead of the film thickness of the entire underlying layer 12 of the laminated structure.

(indium tin oxide layer)

The indium tin oxide layer 13 is amorphous and is crystallized by heat treatment. Since it is amorphous, the etching property is good. Moreover, it is made into a crystal by heat processing, and durability is also favorable. Patterning can be performed by etching, and a portion 13a in which the indium tin oxide layer 13 exists and a portion 13b in which the indium tin oxide layer 13 is not present are provided in the indium tin oxide layer 13. Further, the indium tin oxide layer 13 may have a single layer structure or a laminate structure having two or more layers having different compositions. The indium tin oxide layer 13 is preferably in contact with the underlayer 12 in terms of crystallization by heat treatment.

Furthermore, the amorphous and crystalline forms can be distinguished by the magnitude of the rate of change in resistance. First, the evaluation object was immersed in a HCl solution (concentration: 1.5 mol/L) for 5 minutes. The rate of change in electrical resistance (sheet resistance after immersion/sheet resistance before immersion) was determined from the sheet resistance before and after immersion. A crystal having a resistance change rate of 200% or less is used as a crystal, and an electric resistance change rate exceeding 200% is used as an amorphous material. When the rate of change in resistance is 200% or less, the crystalline portion and the amorphous portion are mixed, and when the rate of change in resistance is about 100%, the crystal is substantially entirely crystallization.

The indium tin oxide layer 13 mainly contains indium tin oxide, which is an oxide of indium and tin. Examples of the oxide constituting the indium tin oxide include indium oxide, tin oxide, a composite oxide of indium oxide and tin oxide, and the like.

It is preferable that the indium tin oxide contains 5% by mass or more and 17% by mass or less of tin in terms of oxide (SnO ₂ , the same applies hereinafter). When the amount of tin is 5 mass% or more in terms of oxide, the sheet resistance at the time of crystallization is lowered. On the other hand, in the case where tin is contained in an amount of 17% by mass or less in terms of oxide, crystallization becomes easy. More preferably, the indium tin oxide contains 6% by mass or more of tin, more preferably 7% by mass or more, and particularly preferably 8% by mass or more. Further, it is more preferable that the indium tin oxide contains 15% by mass or less of tin in terms of oxide.

The indium tin oxide layer 13 is preferably made of only indium tin oxide, but may contain components other than indium tin oxide as needed, without departing from the gist of the present invention. Examples of the component other than the indium tin oxide include oxides of aluminum, zirconium, gallium, germanium, tungsten, zinc, titanium, magnesium, lanthanum, cerium, and the like. The content of the component other than the indium tin oxide layer in the indium tin oxide layer 13 is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, more preferably in the entire indium tin oxide layer 13. It is 1% by mass or less.

The thickness of the indium tin oxide layer 13 is preferably 10 nm or more. When the thickness is 10 nm or more, the crystallization becomes good, and the sheet resistance after crystallization becomes low. The thickness is more preferably 15 nm or more from the viewpoint of crystallization and sheet resistance. On the other hand, the thickness is preferably 40 nm or less in terms of shortening the film formation time and increasing the transmittance. The thickness is more preferably 35 nm or less, and still more preferably 30 nm or less from the viewpoint of film formation time, transmittance, and reflectance difference ΔR.

The indium tin oxide layer 13 is crystallized by heat treatment. The heat treatment can usually be carried out in the atmosphere. The heat treatment temperature is preferably 100 ° C or higher and the heat treatment time is preferably 3 minutes or longer in terms of the crystallization of the indium tin oxide layer 13 being good. On the other hand, in terms of suppressing the damage of the transparent substrate 11, and the productivity is also good, the heat treatment temperature is preferably 170 ° C or lower, and the heat treatment time is preferably 180 minutes or shorter.

The laminated body 10 is preferably a heat treatment, and the reflectance difference ΔR of the indium oxide layer 13 is not more than 1%. As the heat treatment conditions, for example, the heat treatment temperature is 150 ° C, and the heat treatment time is 30 minutes. When the reflectance difference ΔR after the heat treatment is 1% or less, the visibility of the etching pattern formed on the indium tin oxide layer 13 is sufficiently lowered. The reflectance difference ΔR after the heat treatment is more preferably 0.7% or less.

The reflectance difference ΔR is the average reflectance R ₁ at a position of the indium tin oxide layer 13 at a wavelength of 480 nm or more and 650 nm or less at the position of the indium tin oxide layer 13 as the light incident surface of the laminated body 10 after the heat treatment. [%], the absolute value (ΔR = | R _{1 -} R ₂ |) of the difference between the average reflectance R ₂ [%] at a wavelength of 480 nm or more and 650 nm or less at a position where the indium tin oxide layer 13 is not present. . That is, in the case where the indium tin oxide layer 13 is not present, it is preferable that the under layer 12 is present from the viewpoint of the visibility of the etching pattern, or the alkali resistance and the scratch resistance.

The adjustment of the reflectance difference ΔR can be performed by adjusting the thickness, refractive index, and the like of each layer after the heat treatment, and in particular, by adjusting the thickness of the underlayer 12, the refractive index, and the like. As explained, the base layer 12 has a large change in refractive index depending on the ratio of constituent elements. Thereby, regardless of the refractive index of the constituent layer other than the underlayer 12, the refractive index of the entire constituent layer can be easily adjusted.

Next, the conductive laminated body 20 will be described.

FIG. 2 is a cross-sectional view showing an example of the conductive laminated body 20. The conductive laminated body 20 is obtained by heat-treating the laminated body 10. The conductive laminate 20 has, for example, a transparent substrate 11 , a base layer 12 , and a crystalline indium tin oxide layer 21 . The transparent substrate 11 and the underlayer 12 are the same as the transparent substrate 11 and the underlayer 12 in the laminate 10.

Since the indium tin oxide layer 21 is crystalline, the durability is improved. The portion 21a in which the indium tin oxide layer 21 exists and the portion 21b in which the indium tin oxide layer 21 is not present may be provided in the indium tin oxide layer 21 by pattern formation by etching. Examples of the etching pattern include a plurality of transparent electrodes and the like. In the aspect in which crystallization becomes good, the indium tin oxide layer 21 is preferably in contact with the underlayer 12.

The indium tin oxide layer 21 mainly contains indium tin oxide, which is an oxide of indium and tin. Examples of the oxide constituting the indium tin oxide include indium oxide, tin oxide, a composite oxide of indium oxide and tin oxide, and the like. Further, the indium tin oxide layer 21 may have a single layer structure or a laminate structure having two or more layers having different compositions.

The specific resistance of the indium tin oxide layer 21 is preferably 2.8 × 10 ^-4 Ω‧ cm or less. In the case of the above specific resistance, it is preferable for an electronic device. The specific resistance is preferably 2.4 × 10 ^-4 Ω ‧ cm or less, more preferably 2.3 × 10 ^-4 Ω ‧ cm or less.

It is preferable that the indium tin oxide contains 5% by mass or more and 17% by mass or less of tin in terms of oxide. When the amount of tin is 5 mass% or more in terms of oxide, the specific resistance is lowered. On the other hand, when tin is contained in an amount of 17% by mass or less in terms of oxide, crystallization becomes good. More preferably, the indium tin oxide contains 6% by mass or more of tin, more preferably 7% by mass or more, and particularly preferably 8% by mass or more. Further, it is more preferable that the indium tin oxide contains 15% by mass or less of tin in terms of oxide.

The indium tin oxide layer 21 is preferably made of only indium tin oxide, but may contain components other than indium tin oxide as needed, without departing from the gist of the present invention. Examples of the component other than the indium tin oxide include oxides of aluminum, zirconium, gallium, germanium, tungsten, zinc, titanium, magnesium, lanthanum, cerium, and the like. The content of the component other than the indium tin oxide layer in the indium tin oxide layer 21 is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, more preferably in the entire indium tin oxide layer 21. It is 1% by mass or less.

The thickness of the indium tin oxide layer 21 is preferably 10 nm or more. When the thickness is 10 nm or more, crystallization becomes good, and the sheet resistance also becomes low. The thickness is more preferably 15 nm or more from the viewpoint of crystallization and sheet resistance. On the other hand, the thickness is preferably 40 nm or less in terms of shortening the film formation time and increasing the transmittance. The thickness is more preferably 35 nm or less, and still more preferably 30 nm or less from the viewpoint of film formation time, transmittance, and reflectance difference ΔR.

The following reflectance difference ΔR in the conductive laminated body 20 is preferably 1% or less. When the reflectance difference ΔR is 1% or less, the visibility of the etching pattern formed on the indium tin oxide layer 21 is sufficiently low. The reflectance difference ΔR is preferably 0.7% or less.

The reflectance difference ΔR is such that the transparent substrate 11 side serves as a light incident surface, and the average reflectance R ₁ [%] at a position of the indium tin oxide layer 21 at a wavelength of 480 nm or more and 650 nm or less and the absence of indium tin are present. The absolute value (ΔR = | R _{1 -} R ₂ |) of the difference between the average reflectance R ₂ [%] at a wavelength of 480 nm or more and 650 nm or less at the position of the oxide layer 21 . That is, in the case where the indium tin oxide layer 21 is not present, it is preferable that the under layer 12 is present from the viewpoint of the visibility of the etching pattern, or the alkali resistance and the scratch resistance.

The adjustment of the reflectance difference ΔR can be performed by adjusting the thickness, refractive index, and the like of each layer, and in particular, by adjusting the thickness of the underlayer 12, the refractive index, and the like. As explained, the base layer 12 has a large change in refractive index depending on the ratio of constituent elements. Thereby, regardless of the refractive index of the constituent layer other than the underlayer 12, the refractive index of the entire constituent layer can be easily adjusted.

The conductive laminate 20 can be preferably used in an electronic device, and can be preferably used, for example, in an electronic device having a display portion and a touch panel disposed on a front surface of the display portion. The conductive laminate 20 is particularly useful as a substrate having a transparent electrode in a touch panel. Examples of the touch panel include a resistive film type in which a touch position is specified by contact of upper and lower electrodes, and a capacitive coupling method in which a change in electrostatic capacitance is sensed.

Next, a method of manufacturing the laminated body 10 and the conductive laminated body 20 will be described.

The laminated body 10 can be produced by forming the underlying layer 12 on the transparent substrate 11 and then forming the indium tin oxide layer 13. The film formation method is not necessarily limited, and a sputtering method, an ion plating method, a vacuum evaporation method, or a sputtering method is preferable.

The base layer 12 is formed, for example, by sputtering using a sputtering target mainly containing ruthenium. At this time, it is preferred to adjust the ratio of the introduced gas in the following manner.

First, it is preferred to introduce argon gas and oxygen gas to perform pre-sputtering. At this time, it is preferable to adjust the ratio of argon gas to oxygen gas in such a manner that the state of sputtering is in the metal mode or the transition mode. Here, the metal mode and the transition mode are states in which a film that absorbs visible light is formed due to insufficient oxygen. The ratio of oxygen is preferably 0.1% by volume or more, more preferably 0.3% by volume or more, and still more preferably 0.5% by volume or more based on the total amount of argon gas and oxygen gas. Again, oxygen The ratio is preferably 30% by volume or less, more preferably 20% by volume or less, and still more preferably 10% by volume or less based on the total amount of argon gas and oxygen gas.

Next, it is preferred to introduce nitrogen gas while maintaining the ratio of argon gas to oxygen at the above ratio, that is, to introduce argon gas, oxygen gas, and nitrogen gas to perform sputtering. At this time, it is preferable to adjust the ratio of argon gas to nitrogen gas so that the state of sputtering becomes a reaction mode. The reaction mode is a reaction in which ruthenium, oxygen, and nitrogen are reacted, and a film having transparency to visible light should be formed. The ratio of nitrogen gas is preferably 30% by volume or more, more preferably 40% by volume or more, and still more preferably 45% by volume or more based on the total amount of argon gas and nitrogen gas. Further, the ratio of nitrogen gas is preferably less than 50% by volume, more preferably 49.7% by volume or less, and still more preferably 49.5% by volume or less based on the total amount of argon gas and nitrogen gas.

Preferably, in the above manner, the ratio of argon gas to oxygen gas is adjusted in a metal mode or a transition mode when argon gas and oxygen gas are introduced, and argon is adjusted in a reaction mode when argon gas, oxygen gas, and nitrogen gas are introduced. The ratio of gas to nitrogen. By this method, the underlayer 12 which has a large effect of promoting the crystallization of the indium tin oxide layer 13 can be formed.

The indium tin oxide layer 13 is formed by, for example, a sputtering method using a sputtering target containing indium tin oxide. The sputtering target is preferably tin containing 5 mass% or more and 17 mass% or less in terms of oxide in the indium tin oxide. The indium tin oxide in the sputtering target preferably contains a sintered body obtained by mixing tin oxide (SnO ₂ ) and indium oxide (In ₂ O ₃ ) and sintering the same.

The film formation of the indium tin oxide layer 13 is preferably a mixed gas in which, for example, 0.5% by volume or more and 10% by volume or less, preferably 0.8% by volume or more and 6% by volume or less of oxygen is mixed in argon gas. Sputter on one side. By performing sputtering while introducing such a mixed gas, it is possible to form an amorphous film, to perform crystallization by heat treatment, and to have a lower specific resistance after crystallization.

The conductive laminated body 20 can be obtained by heat-treating the laminated body 10. The heat treatment can usually be carried out in the atmosphere. The heat treatment temperature is preferably 100 ° C or higher and the heat treatment time is preferably 3 minutes or longer in terms of the crystallization of the indium tin oxide layer 13 being good. The other side The heat treatment temperature is preferably 170 ° C or less, and the heat treatment time is preferably 180 minutes or less in terms of suppressing damage of the transparent substrate 11 and improving productivity.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples. Examples 1 to 5 are examples of the present invention, and Examples 6 to 9 are comparative examples of the present invention. Furthermore, the invention is not limited by the examples. Moreover, the thickness of each layer is obtained based on optical characteristics, or film formation speed, and the conveyance speed of a base material, and it is not the actual measurement.

(example 1)

The surface of the polyethylene terephthalate film having a thickness of 100 μm was prepared as a transparent substrate. A hafnium oxynitride film (SiO _x N _y film) is formed on the transparent substrate as a base layer. The thickness of the base layer was 10 nm. The base layer has a refractive index of 1.49. The refractive index is a value at a wavelength of 500 nm and is measured by an ellipsometer.

Further, the base layer is formed in the following manner. First, a boron-doped germanium target is used, argon gas and oxygen gas are introduced, and a DC (direct current) pulse power source is used for pre-sputtering. The ratio of oxygen to the total amount of argon and oxygen was 5% by volume. The state of the sputtering at this time is the metal mode or the transition mode.

Thereafter, nitrogen gas was introduced in addition to the above argon gas and oxygen gas. At this time, the ratio of nitrogen gas to the total amount of argon gas and nitrogen gas was set to 45 vol%. Further, the ratio of oxygen to the total amount of argon gas and oxygen gas was set to be the same as that of the pre-sputtering (still 5% by volume). The state of the sputtering at this time is the reaction mode.

While argon gas, oxygen gas, and nitrogen gas were introduced under the above conditions, sputtering was continued to form a base layer on the transparent substrate. The thickness of the underlayer is adjusted by the sputtering rate and the transport speed of the transparent substrate.

After the underlayer was formed, an amorphous indium tin oxide layer (ITO layer) having a thickness of 25 nm was formed on the underlayer to prepare a test piece. The ITO layer is formed by using a target containing 10% by mass of tin indium tin oxide in terms of oxide (10% by mass of tin oxide (SnO ₂ ) and 90% by mass of indium oxide (In ₂ O ₃ ) The target is mixed and sintered, and argon gas and oxygen gas are introduced, and sputtering is performed using a DC power source. The ratio of oxygen to the total amount of argon and oxygen was 1% by volume. The thickness of the ITO layer is adjusted by the sputtering rate and the transport speed of the transparent substrate or the like.

(Example 2)

The underlayer and the ITO layer were formed in the same manner as in Example 1 except that the conditions for forming the underlayer were changed, and the refractive index of the underlayer was changed to 1.59. Further, the formation conditions of the underlayer are as follows. In the introduction of argon gas and oxygen during the pre-sputtering, the ratio of oxygen to the total amount of argon gas and oxygen gas was set to 2% by volume. The state of the sputtering at this time is the metal mode or the transition mode. In the subsequent introduction of argon gas, oxygen gas, and nitrogen gas during sputtering, the ratio of nitrogen gas to the total amount of argon gas and nitrogen gas was set to 48% by volume. Further, the ratio of oxygen to the total amount of argon gas and oxygen gas is set to be the same as that of the pre-sputtering. The state of the sputtering at this time is the reaction mode.

(Example 3)

The underlayer and the ITO layer were formed in the same manner as in Example 1 except that the conditions for forming the underlayer were changed, and the refractive index of the underlayer was changed to 1.80. Further, the formation conditions of the underlayer are as follows. In the introduction of argon gas and oxygen during the pre-sputtering, the ratio of oxygen to the total amount of argon gas and oxygen gas was set to 1% by volume. The state of the sputtering at this time is the metal mode or the transition mode. In the subsequent introduction of argon gas, oxygen gas, and nitrogen gas during sputtering, the ratio of nitrogen gas to the total amount of argon gas and nitrogen gas was set to 49% by volume. Further, the ratio of oxygen to the total amount of argon gas and oxygen gas is set to be the same as that of the pre-sputtering. The state of the sputtering at this time is the reaction mode.

(Example 4)

The underlayer and the ITO layer were formed in the same manner as in Example 1 except that the conditions for forming the underlayer were changed, and the refractive index of the underlayer was changed to 1.95. Further, the formation conditions of the underlayer are as follows. In the introduction of argon and oxygen during pre-sputtering, The ratio of oxygen to the total amount of argon and oxygen was set to 0.5% by volume. The state of the sputtering at this time is the metal mode or the transition mode. In the subsequent introduction of argon gas, oxygen gas, and nitrogen gas during sputtering, the ratio of nitrogen gas to the total amount of argon gas and nitrogen gas was set to 49.5 vol%. Further, the ratio of oxygen to the total amount of argon gas and oxygen gas is set to be the same as that of the pre-sputtering. The state of the sputtering at this time is the reaction mode.

(Example 5)

A base layer and an ITO layer were formed in the same manner as in Example 1 except that the thickness of the ITO layer was changed to 20 nm, and a test piece was prepared.

(Example 6)

A base layer and an ITO layer were formed in the same manner as in Example 1 except that the underlayer was changed to a ruthenium oxide film (SiO ₂ film) to prepare a test piece. Further, the SiO ₂ film was formed by using a boron-doped germanium target, introducing argon gas and oxygen gas, and performing sputtering using a DC pulse power source. The ratio of oxygen to the total amount of argon and oxygen was set to 50% by volume. The state of the sputtering at this time is the reaction mode. The base layer has a refractive index of 1.47.

(Example 7)

A base layer and an ITO layer were formed in the same manner as in Example 1 except that the underlayer was changed to a ruthenium oxide film (Si ₃ N ₄ film) to prepare a test piece. Further, the Si ₃ N ₄ film was formed by using a boron-doped germanium target, introducing argon gas and nitrogen gas, and performing sputtering using a DC pulse power source. The ratio of nitrogen gas to the total amount of argon gas and nitrogen gas was set to 50% by volume. The state of the sputtering at this time is the reaction mode. The base layer has a refractive index of 2.04.

(Example 8)

A base layer and an ITO layer were formed in the same manner as in Example 1 except that the base layer was changed to an aluminum oxide film (Al ₂ O ₃ film) to prepare a test piece. Further, the Al ₂ O ₃ film was formed by using a pure aluminum target, introducing argon gas and nitrogen gas, and performing sputtering using a DC pulse power source. The ratio of nitrogen gas to the total amount of argon gas and nitrogen gas was set to 50% by volume. The state of the sputtering at this time is the reaction mode. The base layer has a refractive index of 2.04.

(Example 9)

A test piece was produced by forming a base layer and an ITO layer in the same manner as in Example 6 except that the thickness of the ITO layer was changed to 20 nm.

Next, the test pieces of the respective examples were heat-treated at 150 ° C for 30 minutes in the atmosphere. The following evaluation was performed on the heat-treated test piece. The results are shown in Table 1. Further, in the table, the flow ratios of Examples 1 to 5 are ratios of oxygen (oxygen) to the total amount of oxygen and oxygen when argon gas and oxygen gas are introduced during pre-sputtering. Further, in the table, the flow ratios (nitrogen) of Examples 1 to 5 are ratios of nitrogen gas to total amount of argon gas and nitrogen gas when argon gas, oxygen gas, and nitrogen gas are introduced during sputtering.

[Sheet resistance, specific resistance]

The test piece before and after the heat treatment was cut into a size of 10 mm × 10 mm, and the sheet resistance of the ITO layer was measured using a Hall effect measurement system (Nanometrics Co., Ltd., type: HL5500PC). Using the sheet resistance, the specific resistance of the ITO layer was determined by the following formula (1).

Specific resistance [Ω‧cm] = sheet resistance value [Ω / □] × thickness of ITO layer [cm] ... (1)

[resistance change rate]

The heat-treated test piece was immersed in a HCl solution (concentration: 1.5 mol/L) for 5 minutes. The rate of change in electrical resistance (sheet resistance after immersion/sheet resistance before immersion × 100 [%]) was determined from the sheet resistance of the ITO layer before and after immersion. If the ITO layer is crystalline and the etching rate is slow, the rate of change in resistance is close to 100%. On the other hand, if the ITO layer is amorphous and the etching rate is fast, the rate of change in resistance is as large as more than 200%. Further, the rate of change in the resistance value of the ITO layer was measured in the same manner for the test piece before the heat treatment. As a result, it was confirmed that the rate of change in electric resistance exceeded 200%, and all of them were amorphous. Further, the sheet resistance was measured by the above method.

As shown in Examples 1 to 5, in the case of having a base layer containing ruthenium, oxygen, and nitrogen, the rate of change in electrical resistance of the ITO layer after heat treatment was small, and the ITO layer was sufficiently crystallized. Further, in the case of having the above-mentioned underlayer, the sheet resistance of the ITO layer after the heat treatment is also small. In particular, as in the case of Example 5, even when the ITO layer was thin, the ITO layer was sufficiently crystallized, and the sheet resistance was also small. Further, in the case of the above-mentioned underlayer, a refractive index of a large range of 1.49 or more and 1.95 or less can be obtained. Therefore, when an etching pattern is formed on the ITO layer, it becomes easy to reduce the visibility of the etching pattern formed on the ITO layer together with other layers.

Further, composition analysis of the underlayers 12 of Examples 1 to 5 in which the effect of reducing the sheet resistance was observed by photoelectron spectroscopy was carried out. As a result, the ratio of the number of molecules of N ₂ /O _{2 in} the underlayer 12 of Examples 1 to 5 was 0.05 or more and 3.6 or less. For example, the molecular ratio of N ₂ /O ₂ of Example 1 is 0.06, the molecular ratio of N ₂ /O ₂ of Example 2 is 0.07, and the molecular ratio of N ₂ /O ₂ of Example 3 is 1.4, Example 4 The molecular ratio of N ₂ /O ₂ was 3.6.

Next, the following test piece was assumed, and the visibility of the etching pattern formed on the ITO layer was evaluated by calculation. Further, Example 10 is an example of the present invention, and Example 11 is a comparative example of the present invention.

(Example 10)

The transparent substrate is set to have a refractive index of 1.53 for light having a wavelength of 500 nm and is a thickness. 100 μm polyethylene terephthalate film. A urethane urethane containing a titanium oxide filler was deposited as a primer coating on the transparent substrate in a thickness of 1 μm. The primer coating has a refractive index of 1.55 for light having a wavelength of 500 nm.

A first yttria layer having a refractive index of 1.70 for light having a wavelength of 500 nm was deposited on the primer coating layer so as to have a thickness of 47 nm. Further, a second yttria layer having a refractive index of 1.50 for light having a wavelength of 500 nm was deposited on the first yttrium oxynitride layer so as to have a thickness of 20 nm. Here, the underlayer includes a first hafnium oxynitride layer and a second hafnium oxynitride layer. An ITO layer having a refractive index of 1.83 for light having a wavelength of 500 nm was deposited on the underlayer so as to have a thickness of 25 nm.

For such a test piece, the reflectance difference ΔR was calculated. The calculation assumes a vacuum (refractive index of 1) between the light source and the test piece, and between the test piece and the tester, and assumes that the normal line of the test piece and the direction of travel of the light are at an angle of 0 degrees, and the light It was incident on the test piece from the side of the transparent substrate. Further, there is no portion in which the ITO layer for determining the average reflectance R ₂ is formed to include a transparent substrate and a base layer. As a result, the reflectance difference ΔR was 0.02%.

(Example 11)

A test piece similar to that of Example 10 was produced except that the constitution of the underlayer was changed. The underlayer is a ruthenium oxide layer having a refractive index of 1.47 and a thickness of 30 nm for light having a wavelength of 500 nm. The reflectance difference ΔR was calculated in the same manner as in Example 11. As a result, the reflectance difference ΔR was 1.35%.

10‧‧‧Layer

11‧‧‧Transparent substrate

12‧‧‧ basal layer

13‧‧‧Amorphous indium tin oxide layer

13a‧‧‧ Part of the indium tin oxide layer 13

13b‧‧‧There is no part of the indium tin oxide layer 13

Claims (9)

A laminate comprising: a transparent substrate; a base layer laminated on the transparent substrate and containing germanium, oxygen, and nitrogen; and a layer of the underlying layer and mainly containing amorphous indium tin oxide After the heat treatment temperature is 150° C. and the heat treatment time is 30 minutes, the heat treatment temperature is 150° C., and when the transparent substrate side is used as the light incident surface, the indium tin oxide layer is located at a wavelength of 480 nm or more. 650nm or less and an average reflectance of R ₁ [%], the absolute value of the difference between the position of the indium tin oxide layer is not present in a wavelength of 480nm or more and 650nm or less of the average reflectivity R ₂ [%] of the reflectivity i.e. The difference ΔR is 1% or less. The laminate according to claim 1, wherein the base layer is in contact with the indium tin oxide layer. The laminate according to claim 1 or 2, wherein the indium tin oxide layer has a thickness of 40 nm or less. The laminate according to any one of claims 1 to 3, wherein the indium tin oxide layer contains 5% by mass or more and 17% by mass or less of tin in terms of an oxide. A conductive laminate comprising: a transparent substrate; a base layer laminated on the transparent substrate and containing ruthenium, oxygen, and nitrogen; and an indium tin oxide laminated on the base layer and mainly containing crystalline The indium tin oxide layer of the material has an average reflectance R ₁ [%] at a position of the indium tin oxide layer at a wavelength of 480 nm or more and 650 nm or less when the transparent substrate side is used as a light incident surface. The absolute value of the difference between the average reflectance R ₂ [%] at a wavelength of 480 nm or more and 650 nm or less at a position where the indium tin oxide layer is not present is a reflectance difference ΔR of 1% or less. The laminate according to claim 5, wherein the base layer is in contact with the indium tin oxide layer. The conductive laminate of claim 5 or 6, wherein the indium tin oxide layer has a thickness of 40 nm or less. The conductive laminate according to any one of claims 5 to 7, wherein the indium tin oxide layer contains 5% by mass or more and 17% by mass or less of tin in terms of an oxide. An electronic machine having the electroconductive laminate according to any one of claims 5 to 8.