WO2015151677A1 - Transparent conductive member and method for producing transparent conductive member - Google Patents

Abstract

This transparent conductive member is configured so as to be provided with a first dielectric layer, a second dielectric layer, and a metal layer that is formed between the first dielectric layer and the second dielectric layer. This transparent conductive member is also configured such that the first dielectric layer and the second dielectric layer contain an infrared absorbing compound.

Description

Transparent conductive member and method for manufacturing transparent conductive member

The present invention relates to a transparent conductive member having a metal layer and a dielectric layer, and a method for manufacturing the transparent conductive member.

In recent years, low resistance transparent conductive films are required for various devices such as touch panel materials, liquid crystal displays, plasma displays, inorganic and organic EL (electroluminescence) displays, and solar cells. As a material constituting such a transparent conductive film, for example, metals such as Au, Ag, Pt, Cu, Rh, Pd, Al, Cr, In ₂ O ₃ , CdO, CdIn ₂ O ₄ , Cd ₂ SnO _{4 are used.} , TiO ₂ , SnO ₂ , ZnO, ITO (indium tin oxide) and other oxide semiconductors are known.

Further, in a touch panel type display device or the like, a wiring made of a transparent conductive film or the like is disposed on the image display surface of the display element. For this reason, the transparent conductive film is required to have high light transmittance. Conventionally, a transparent conductive film made of ITO having a high light transmittance is often used in such various display devices.

In recent years, a capacitive touch panel display device has been developed, and the surface electrical resistance of the transparent conductive film is further reduced, specifically, 50Ω / sq. The following resistance values are strongly demanded. However, a conventionally used ITO film has a resistance value of 150 Ω / sq. However, the characteristics were insufficient for the above demand.

Against this background, in recent years, development of a next-generation transparent conductive film that replaces ITO has been actively conducted. For example, a transparent conductive member has been proposed that aims to achieve both transparency and conductivity by forming layers having a high refractive index on both surfaces of silver serving as a conductive layer (see, for example, Patent Document 1). .

JP-A-9-171717

However, in the case of a capacitive touch panel, it is necessary to perform pattern etching. Therefore, in the transparent conductive member configured to form a high refractive index layer on both sides of the above-described silver, two high refractive index layers and silver It is necessary to simultaneously etch three or more layers with the layer.

When performing etching by photolithography, it is difficult to select an appropriate etchant and to match the etching process to etch three layers of different materials at once. Further, in the case of pattern etching by laser etching, it is difficult to apply because all the layers to be etched need to absorb the laser wavelength.
Thus, in the transparent conductive member having different types of laminates such as a conductive layer and a high refractive index layer, a decrease in productivity in the etching process is a problem.

In order to solve the above-described problems, the present invention provides a transparent conductive member having high productivity and a method for producing the transparent conductive member.

The transparent conductive member of the present invention includes a first dielectric layer, a second dielectric layer, and a metal layer formed between the first dielectric layer and the second dielectric layer. The first dielectric layer and the second dielectric layer contain an infrared absorbing compound.

The transparent conductive member manufacturing method of the present invention includes a step of forming a first dielectric layer containing an infrared absorbing compound, a step of forming a metal layer on the first dielectric layer, and a metal layer. Forming a second dielectric layer containing an infrared absorbing compound.

In the above-described transparent conductive member and transparent conductive member manufacturing method, the first dielectric layer and the second dielectric layer contain an infrared absorbing compound. For this reason, by irradiating the laser beam, the first dielectric layer and the second dielectric layer containing the infrared absorbing compound can be etched together with the metal layer. For this reason, by using the transparent conductive member having this configuration, it is possible to easily perform pattern formation of the conductive region and the non-conductive region. That is, a transparent conductive member having high productivity can be provided by forming the transparent conductive member having the above-described configuration.

According to the present invention, it is possible to provide a transparent conductive member having high productivity and a method for producing the transparent conductive member.

It is a figure which shows the structure of the transparent conductive member of 1st Embodiment. It is a figure which shows the structure of the transparent conductive member of 1st Embodiment. It is a figure which shows the structure of the transparent conductive member of 2nd Embodiment. It is a figure which shows the structure of the transparent conductive member of 2nd Embodiment (modification). It is a schematic diagram which shows the example of a process which manufactures a transparent conductive member by an online process. It is a perspective view which shows an example of a structure of the touchscreen to which a transparent conductive member is applied.

Hereinafter, although the example of the form for implementing this invention is demonstrated, this invention is not limited to the following examples.
The description will be given in the following order.
1. Embodiment of transparent conductive member (first embodiment)
2. Embodiment of transparent conductive member (second embodiment)
3. Method for manufacturing transparent conductive member (third embodiment)
4). Electronic devices

<1. Embodiment of Transparent Conductive Member (First Embodiment)>
Hereinafter, specific embodiments of the transparent conductive member of the present invention will be described. 1 and 2 show a schematic configuration (cross-sectional view) of the transparent conductive member of the first embodiment.

[Basic configuration of transparent conductive member]
The transparent conductive member 10 having the configuration shown in FIG. 1 has a configuration in which a first dielectric layer 12, a metal layer 13, and a second dielectric layer 14 are laminated in this order. A transparent conductive member 10 is provided on the transparent substrate 11.

Further, in the transparent conductive member 10 shown in FIG. 2, a part of the laminated body including the first dielectric layer 12, the metal layer 13, and the second dielectric layer 14 provided on the transparent substrate 11 is subjected to pattern etching. Shows the state.
By this pattern etching, the first dielectric layer 12, the metal layer 13, and the second dielectric layer 14 are removed, and the surface of the transparent substrate 11 is exposed from the surface side of the second dielectric layer 14. 15 is provided. By providing the opening 15 in this manner, a transparent region having a conductive region 16 in which the metal layer 13 is continuously formed and a non-conductive region 17 in which the metal layer 13 is not formed and having a desired conductive layer pattern is provided. The conductive member 10 can be formed.
In the transparent conductive member 10 shown in FIG. 1, the metal layer 13 is formed on the entire surface of the transparent substrate 11. Therefore, the entire region where the metal layer 13 is formed is the conduction region 16.
Hereinafter, the detail of each structure of the transparent conductive member 10 is demonstrated.

[Metal layer]
The metal layer 13 is a layer containing a metal for conducting electricity in the transparent conductive member 10. The metal layer 13 may be formed on the entire surface of the transparent substrate 11 as shown in FIG. 1, or may be patterned into a desired shape as shown in FIG.

The metal contained in the metal layer 13 is not particularly limited as long as it is a highly conductive metal, and examples thereof include silver, copper, gold, platinum group, titanium, and chromium. The metal layer 13 may contain only one kind of these metals or two or more kinds.

From the viewpoint of high conductivity, the metal contained in the metal layer 13 is preferably silver or an alloy containing 90 atomic% or more of silver. Examples of the metal combined with silver include zinc, gold, copper, palladium, aluminum, manganese, bismuth, neodymium, and molybdenum. For example, a combination of silver and zinc is preferable because the sulfidation resistance of the metal layer 13 is increased. A combination of silver and gold is preferable because salt resistance (NaCl) resistance is increased. Furthermore, when silver and copper are combined, oxidation resistance is increased, which is preferable.

The plasmon absorption rate of the metal layer 13 is preferably 10% or less, more preferably 7% or less, and further preferably 5% or less over the wavelength range of 400 to 800 nm (over the entire range). If there is a region having a large plasmon absorption rate in a part of the wavelength of 400 to 800 nm, the transmitted light of the conductive region 16 of the transparent conductive member 10 is likely to be colored.

The plasmon absorption rate at a wavelength of 400 to 800 nm of the metal layer 13 is measured by the following procedures (i) to (iii).

(I) On a glass substrate, platinum palladium is formed to a thickness of 0.1 nm by a BMC-800T vapor deposition apparatus manufactured by SYNCHRON. The average thickness of platinum palladium is calculated from the formation rate of the manufacturer's nominal value of the vapor deposition apparatus. Thereafter, a metal layer having a thickness of 20 nm is formed on the substrate to which platinum palladium is adhered by vacuum deposition.

(Ii) Measuring light is incident from an angle inclined by 5 ° with respect to the normal of the surface of the obtained metal layer, and the transmittance and reflectance of the metal layer are measured. Then, [absorbance = 100− (transmittance + reflectance)] is calculated from the transmittance and reflectance at each wavelength, and this is used as reference data. The transmittance and reflectance are measured with a spectrophotometer.

(Iii) Subsequently, a metal layer to be measured is formed on the same glass substrate. And the transmittance | permeability and a reflectance are similarly measured about the said metal layer. The reference data is subtracted from the obtained absorption rate, and the calculated value is defined as the plasmon absorption rate of the metal layer.

The thickness of the metal layer 13 is preferably 10 nm or less, more preferably in the range of 3 to 9 nm, and still more preferably in the range of 5 to 8 nm. In the transparent conductive member 10, when the thickness of the metal layer 13 is 10 nm or less, the metal layer 13 is less likely to reflect the original metal. Furthermore, when the thickness of the metal layer 13 is 10 nm or less, the optical admittance of the transparent conductive member 10 by the first dielectric layer 12 and the second dielectric layer 14 can be easily adjusted, and light on the surface of the conductive region 16 can be adjusted. It is easy to suppress reflection. The thickness of the metal layer 13 can be obtained by measurement using an ellipsometer.

The metal layer 13 may be a layer formed by any method, but is preferably a layer formed by a vacuum deposition method. If it is a vacuum evaporation method, the transparent substrate 11 will not be exposed to a high temperature environment, but the metal layer 13 with high planarity can be formed very quickly.

On the other hand, when the metal layer 13 is a layer formed on an underlayer described later, the underlayer becomes a growth nucleus when the metal layer 13 is formed, so that the metal layer 13 tends to be a smooth film. As a result, even if the metal layer 13 is thin, plasmon absorption hardly occurs.

Further, when the metal layer 13 is a layer patterned into a desired shape, the patterning method is not particularly limited. For example, the metal layer 13 may be a layer formed by arranging a mask having a desired pattern, or may be a layer patterned by a known etching method.

[First dielectric layer, second dielectric layer]
The first dielectric layer 12 and the second dielectric layer 14 are layers that adjust the light transmittance (optical admittance) of the conductive region 16 of the transparent conductive member 10, that is, the region where the metal layer 13 is formed. At least the conductive region 16 of the transparent conductive member 10 is formed. Although the first dielectric layer 12 and the second dielectric layer 14 may be formed also in the non-conductive region 17 of the transparent conductive member 10, a pattern composed of the conductive region 16 and the non-conductive region 17 is visually recognized. From the viewpoint of making it difficult, it is preferably formed only in the conductive region 16 and removed from the non-conductive region 17 as shown in FIG.

The first dielectric layer 12 and the second dielectric layer 14 contain an infrared absorbing compound.
Examples of the infrared absorbing compound included in the first dielectric layer 12 and the second dielectric layer 14 include ZnO, AZO, IZO, GZO, tin oxide, ATO, ITO, lanthanum boride, and nickel complex. Systemic compounds and the like can be used. Specific product names include: zinc oxide series, Cellax series (manufactured by Nissan Chemical Industries, Ltd.), passet series (manufactured by Hakusui Tech Co., Ltd.), tin oxide series, ATO dispersion, ITO dispersion (manufactured by Mitsubishi Materials) And KH series (manufactured by Sumitomo Metal Mining Co., Ltd.).
In addition, as the infrared absorbing compound contained in the first dielectric layer 12 and the second dielectric layer 14, an organic compound such as an imonium compound, a phthalocyanine compound, or an aminium compound can be used. Specific product names include NIR-IM1, NIR-AM1 (manufactured by Nagase Chemitex), Lumogen series (manufactured by BASF), and the like.

Further, the first dielectric layer 12 and the second dielectric layer 14 include a dielectric material having a refractive index higher than that of the transparent substrate 11 described later, or an oxide semiconductor material. The refractive index of light having a wavelength of 570 nm of the dielectric material or the oxide semiconductor material is preferably 0.1 to 1.1 larger than the refractive index of light having a wavelength of 570 nm of the transparent substrate 11, and 0.4 to 1 It is more preferable that the value be larger by 0.0. In addition, the value of the refractive index measured in a 25 degreeC environment is used for a refractive index. The refractive index can be determined by measuring using a commercially available ellipsometer.

The specific refractive index of light having a wavelength of 570 nm of the dielectric material or oxide semiconductor material included in the first dielectric layer 12 and the second dielectric layer 14 is preferably greater than 1.5. It is more preferably from 7 to 2.5, still more preferably from 1.8 to 2.5. When the refractive index of the dielectric material or the oxide semiconductor material is larger than 1.5, the first dielectric layer 12 and the second dielectric layer 14 cause the optical admittance of the conductive region 16 of the transparent conductive member 10. Is fully adjusted. In addition, the refractive index of the 1st dielectric material layer 12 and the 2nd dielectric material layer 14 is adjusted with the refractive index of the material contained, and the density of material.

The first dielectric layer 12 and the second dielectric layer 14 include zinc sulfide, metal oxide, inorganic oxide, a mixture of zinc sulfide and metal oxide, a mixture of zinc sulfide and inorganic oxide, titanium oxide ( TiO ₂ ), gallium-doped tin oxide (GZO), zinc oxide (ZnO), aluminum-doped zinc oxide, antimony-doped tin oxide (ATO), antimony-doped zinc oxide (AZO), indium-doped tin oxide (ITO) ), Indium-doped zinc oxide (IZO), or the like can be used.

Examples of the metal oxide and inorganic oxide that can be used together with zinc sulfide include TiO ₂ , ITO (indium tin oxide), ZnO, Nb ₂ O ₅ , ZrO ₂ , CeO ₂ , Ta ₂ O ₅ , and Ti ₃ O. ₅ , Ti ₄ O ₇ , Ti ₂ O ₃ , TiO, SnO ₂ , La ₂ Ti ₂ O ₇ , (indium / zinc oxide), AZO (Al-doped ZnO), GZO (Ga-doped ZnO), ATO (Sb-doped) SnO), ICO (Indium Cerium Oxide), Bi ₂ O ₃ , a-GIO, Ga ₂ O ₃ , GeO ₂ , SiO ₂ , Al ₂ O ₃ , HfO ₂ , SiO, MgO, Y ₂ O ₃ , WO ₃ , And a-GIO (amorphous oxide composed of gallium, indium, and oxygen). Among the inorganic oxides, silicon dioxide (SiO ₂ ) is particularly preferable.

Further, a metal fluoride can be used for the first dielectric layer 12 and the second dielectric layer 14. Examples of the metal fluoride include LaF ₃ , BaF ₂ , Na ₅ Al ₃ F ₁₄ , Na ₃ AlF ₆ , AlF ₃ , MgF ₂ , CaF ₂ , CeF ₃ , NdF ₃ , and YF ₃ .

Further, metal nitride can be used for the first dielectric layer 12 and the second dielectric layer 14. Examples of the metal nitride include boron nitride, aluminum nitride, chromium nitride, silicon nitride, tungsten nitride, magnesium nitride, molybdenum nitride, lithium nitride, and titanium nitride.

The first dielectric layer 12 and the second dielectric layer 14 preferably contain at least zinc sulfide (ZnS) as a dielectric material. Since the first dielectric layer 12 and the second dielectric layer 14 contain zinc sulfide, moisture from the transparent substrate 11 side or the like passes through the first dielectric layer 12 and the second dielectric layer 14. It becomes difficult and corrosion of the metal layer 13 is suppressed.

In the transparent conductive member 10, the first dielectric layer 12 and the second dielectric layer 14 are at least one selected from metal oxides, inorganic oxides, metal fluorides, and metal nitrides together with zinc sulfide. By co-evaporating this compound, the first dielectric layer 12 and the second dielectric layer 14 are likely to be amorphous, and the flexibility of the transparent conductive member 10 is likely to be enhanced.

In the first dielectric layer 12 and the second dielectric layer 14, the average content of zinc sulfide is within the range of 0.5 to 99 mass% with respect to the total number of moles of the material constituting the layer. It is preferably within a range of 50 to 95% by mass, and more preferably within a range of 60 to 85% by mass. When the ratio of zinc sulfide is high, the co-evaporation rate is increased, and the formation rate of the first dielectric layer 12 and the second dielectric layer 14 is increased. Moreover, when the ratio of zinc sulfide is high, the refractive index is increased, and light absorption in the metal layer 13 can be reduced. On the other hand, when many components other than zinc sulfide are contained, the amorphousness of the first dielectric layer 12 and the second dielectric layer 14 is increased, and the first dielectric layer 12 and the second dielectric layer are increased. The occurrence of 14 cracks is suppressed.

The thickness _{T A} of the first dielectric layer 12, preferably in the range of 10 ~ 150 nm, more preferably in the range of 10 ~ 80 nm. Similarly, the second dielectric layer 14 thickness _{T B} is preferably in the range of 10 ~ 150 nm, more preferably in the range of 10 ~ 80 nm.
When the thicknesses of the first dielectric layer 12 and the second dielectric layer 14 are 10 nm or more, the conductive regions 16 of the transparent conductive member 10 are formed by the first dielectric layer 12 and the second dielectric layer 14. The optical admittance is sufficiently adjusted. On the other hand, if the thickness of the first dielectric layer 12 and the second dielectric layer 14 is 150 nm or less, the light in the region where the first dielectric layer 12 and the second dielectric layer 14 are formed. The permeability is difficult to decrease. The thicknesses of the first dielectric layer 12 and the second dielectric layer 14 are measured with an ellipsometer.

The first dielectric layer 12 and the second dielectric layer 14 are preferably formed by a co-evaporation method. Examples of the vapor deposition method include a resistance heating vapor deposition method, an electron beam vapor deposition method, an ion plating method, and an ion beam vapor deposition method. As the vapor deposition apparatus, for example, a BMC-800T vapor deposition machine manufactured by SYNCHRON Co., Ltd. can be used.

When the first dielectric layer 12 is a layer that does not contain zinc sulfide, the second dielectric layer 14 is selected from zinc sulfide, metal oxide, inorganic oxide, metal fluoride, and metal nitride. It is preferable to form a layer formed by co-evaporation with at least one compound. The first dielectric layer 12 and the second dielectric layer 14 are both co-evaporated with zinc sulfide and at least one compound selected from metal oxide, inorganic oxide, metal fluoride and metal nitride. It may be a layer formed by a method.

[Transparent substrate]
As the transparent substrate 11, materials applied to transparent substrates of various display devices can be used.

The transparent substrate 11 is a glass substrate, a cellulose ester resin (for example, triacetyl cellulose (abbreviation: TAC), diacetyl cellulose, acetylpropionyl cellulose, etc.), a polycarbonate resin (for example, Panlite, Multilon (manufactured by Teijin Ltd.)). , Cycloolefin resins (for example, ZEONOR (manufactured by ZEON CORPORATION), ARTON (manufactured by JSR), APPEL (manufactured by Mitsui Chemicals)), acrylic resins (for example, polymethyl methacrylate, acrylite (manufactured by Mitsubishi Rayon), Sumipex) (Manufactured by Sumitomo Chemical Co., Ltd.)), polyimide, phenol resin, epoxy resin, polyphenylene ether (abbreviation: PPE) resin, polyester resin (for example, polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN)), polyether Rusulfone resin, acrylonitrile / butadiene / styrene resin (abbreviation: ABS resin) / acrylonitrile / styrene resin (abbreviation: AS resin), methyl methacrylate / butadiene / styrene resin (abbreviation: MBS resin), polystyrene, methacrylic resin, polyvinyl alcohol / ethylene A transparent resin film made of vinyl alcohol resin (abbreviation: EVOH), styrene block copolymer resin, or the like can be used, and glass can also be used. When the transparent substrate 11 is a transparent resin film, the film may contain two or more kinds of resins.

From the viewpoint of achieving high transparency, the transparent substrate 11 to be applied includes a glass substrate, a cellulose ester resin, a polycarbonate resin, a polyester resin (particularly polyethylene terephthalate), a triacetyl cellulose, a cycloolefin resin, a phenol resin, Consists of resin components such as epoxy resin, polyphenylene ether (PPE) resin, polyethersulfone, ABS / AS resin, MBS resin, polystyrene, methacrylic resin, polyvinyl alcohol / EVOH (ethylene vinyl alcohol resin), styrene block copolymer resin, etc. It is preferable that it is a film.

The transparent substrate 11 preferably has high transparency to visible light, and the average transmittance of light having a wavelength of 450 to 800 nm is preferably 70% or more, more preferably 80% or more, and 85% or more. More preferably it is. When the average light transmittance of the transparent substrate 11 is 70% or more, the light transmittance of the transparent conductive member 10 is likely to be increased. The average absorption rate of light with a wavelength of 450 to 800 nm of the transparent substrate 11 is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less.

The average transmittance is measured by making light incident from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent substrate 11. On the other hand, the average absorptance is measured by measuring the average reflectance of the transparent substrate 11 by making light incident from the same angle as the average transmittance.
Average absorptivity = 100− (average transmittance + average reflectance)
Calculate as The average transmittance and the average reflectance can be measured using a spectrophotometer (for example, U4100: manufactured by Hitachi High-Technologies Corporation).

The refractive index of light having a wavelength of 570 nm of the transparent substrate 11 is preferably in the range of 1.30 to 1.95, more preferably in the range of 1.35 to 1.75, and still more preferably 1.35. Within the range of ~ 1.70. The refractive index of the transparent substrate 11 is usually determined by the material of the transparent substrate 11. The refractive index of the transparent substrate 11 can be determined by measuring in an environment of 25 ° C. using an ellipsometer.

The haze value of the transparent substrate 11 is preferably in the range of 0.01 to 2.5, and more preferably in the range of 0.1 to 1.2. It is preferable that the haze value of the transparent substrate is 2.5 or less because the haze value as the transparent conductive member can be suppressed. The haze value can be measured using a haze meter.

The thickness of the transparent substrate 11 is preferably in the range of 1 μm to 20 mm, more preferably in the range of 10 μm to 2 mm. If the thickness of the transparent substrate 11 is 1 μm or more, the strength of the transparent substrate 11 is increased, and it is possible to prevent the first dielectric layer 12 from being cracked or torn during production. On the other hand, if the thickness of the transparent substrate 11 is 20 mm or less, sufficient flexibility of the transparent conductive member 10 can be obtained. Furthermore, the thickness of the electronic device apparatus etc. which comprised the transparent conductive member 10 can be made thin. Moreover, the electronic device apparatus etc. using the transparent conductive member 10 can also be reduced in weight.

The transparent substrate 11 is preferably used in a forming step after removing moisture and remaining solvent contained in the substrate in advance using a cryopump or the like before forming each constituent layer.

Further, a known clear hard coat (CHC) layer may be provided on the transparent substrate 11 from the viewpoints of hardness, smoothness, and oligomer activity prevention of the first dielectric layer 12 to be formed later. Further, from the viewpoint of the function of the back surface of the transparent substrate 11, a CHC layer may be provided on the back surface of the transparent substrate 11.
As the CHC layer, thermosetting silicon, epoxy, acrylic, or polysilazane can be used, but any CHC layer may be used as long as hardness, smoothness, haze, and adhesion with the upper layer are obtained. However, it is preferable to use an ultraviolet curable acrylic resin from the viewpoint of productivity and safety.
The film thickness of the CHC layer is preferably 0.1 μm or more and 10 μm or less in consideration of the balance of curl, hardness, and cracking.

[Other component layers]
(Underlayer)
The transparent conductive member 10 may include an underlayer that becomes a growth nucleus when the metal layer 13 is formed, as necessary. The underlayer is a layer formed on the transparent substrate 11 side of the metal layer 13 and adjacent to the metal layer 13, and the metal layer 13 is preferably formed directly on the underlayer.
The underlayer is preferably formed at least in the conductive region 16 of the transparent conductive member, and may be formed in the non-conductive region 17 of the transparent conductive member 10.

When the transparent conductive member 10 has a base layer, the smoothness of the surface of the metal layer 13 is increased even when the metal layer 13 is thin. The reason is as follows.

When the material of the metal layer 13 is deposited on the first dielectric layer 12 by a general vacuum deposition method, for example, atoms attached on the first dielectric layer 12 migrate (move) at the initial stage of formation. , Forming a mass (sea-island structure) where atoms gather together. And a film grows clinging to this lump. Therefore, in the film at the initial stage of formation, there is a gap between the lumps, and the film is not conductive. When a lump further grows from this state, a part of the lump is connected and barely conducted. However, since there is still a gap between the lumps, plasmon absorption occurs. As the formation proceeds further, the lumps are completely connected and plasmon absorption is reduced. However, on the other hand, the intrinsic reflection of the metal occurs, and the light transmittance of the film decreases.

On the other hand, when a base layer made of a metal that is difficult to migrate is formed on the first dielectric layer 12, the metal layer 13 grows using the base layer as a growth nucleus. That is, the material of the metal layer 13 is difficult to migrate, and the film grows without forming the above-described sea-island structure. As a result, it becomes easy to obtain a smooth metal layer 13 even if the thickness is small.

The underlayer preferably contains palladium, molybdenum, zinc, germanium, niobium or indium, an alloy of these metals with other metals, an oxide or sulfide of these metals (for example, ZnS). . The underlayer may contain only one kind or two or more kinds.

The amount of palladium, molybdenum, zinc, germanium, niobium or indium contained in the underlayer is preferably 20% by mass or more, more preferably 40% by mass or more, and further preferably 60% by mass or more. When the metal is contained in the base layer in an amount of 20% by mass or more, the affinity between the base layer and the metal layer 13 increases, and the adhesion between the base layer and the metal layer 13 tends to increase. It is particularly preferable that the underlayer contains palladium or molybdenum.

On the other hand, the metal that forms an alloy with palladium, molybdenum, zinc, germanium, niobium, or indium is not particularly limited. For example, a platinum group other than palladium, gold, cobalt, nickel, titanium, aluminum, chromium, and the like can be used.

The thickness of the underlayer is preferably 3 nm or less, more preferably 0.5 nm or less, and particularly preferably a monoatomic film. The underlayer may be in a state where metal atoms are separated from each other and attached to the surface to be formed. If the adhesion amount of the underlayer is 3 nm or less, the underlayer is unlikely to affect the light transmittance and optical admittance of the transparent conductive member 10. The presence or absence of the underlayer is confirmed by the ICP-MS method. Further, the thickness of the underlayer is calculated from the product of the formation speed and the formation time.

The underlayer is preferably a layer formed by vapor deposition or sputtering. The vapor deposition method includes a vacuum vapor deposition method, an electron beam vapor deposition method, an ion plating method, an ion beam vapor deposition method and the like. The deposition time is appropriately selected according to the desired thickness of the underlying layer and the formation speed. The deposition rate is preferably 0.01 to 1.5 nm / second, more preferably 0.01 to 0.7 nm / second.

When the ground layer is a layer patterned into a desired shape, the patterning method is not particularly limited. The underlayer may be, for example, a layer formed in a pattern by a vapor phase forming method by placing a mask having a desired pattern on the surface to be formed, or a layer patterned by a known etching method. There may be. Further, the metal film 13, the first dielectric layer 12, and the second dielectric layer 14 may be patterned by laser etching simultaneously.

(Low refractive index layer)
The transparent conductive member 10 may have a low refractive index layer (not shown) for adjusting the light transmittance (optical admittance) of the conductive region 16 of the transparent conductive member 10 on the second dielectric layer 14. Good. The low refractive index layer may be formed only in the conductive region 16 of the transparent conductive member 10, or may be formed in both the conductive region 16 and the non-conductive region 17 of the transparent conductive member 10.

The low refractive index layer includes a dielectric material that is included in the first dielectric layer 12 and the second dielectric layer 14, or a dielectric material having a refractive index of light having a wavelength of 570 nm lower than that of the oxide semiconductor material, or And oxide semiconductor materials. The refractive index of light with a wavelength of 570 nm of the dielectric material or oxide semiconductor material contained in the low refractive index layer is the refraction of light with a wavelength of 570 nm of the material contained in the first dielectric layer 12 and the second dielectric layer 14. The ratio is preferably 0.2 or more and more preferably 0.4 or more, respectively.

[Physical properties of transparent conductive members]
The average transmittance of light having a wavelength of 450 to 800 nm of the transparent conductive member 10 is preferably 83% or more in both the conductive region 16 and the non-conductive region 17, more preferably 85% or more, and still more preferably. It is 88% or more. When the average transmittance in the above wavelength range is 83% or more, the transparent conductive member 10 can be applied to applications requiring high transparency to visible light.

On the other hand, the average transmittance of light having a wavelength of 400 to 1000 nm of the transparent conductive member 10 is preferably 80% or more in both the conductive region 16 and the non-conductive region 17, more preferably 83% or more, and still more preferably. 85% or more. When the average transmittance of light having a wavelength of 400 to 1000 nm is 80% or more, the transparent conductive member 10 is used in applications requiring transparency with respect to light in a wide wavelength range, such as a transparent conductive film for solar cells. Can be applied.

The average absorptance of light having a wavelength of 400 to 800 nm of the transparent conductive member 10 is preferably 10% or less, more preferably 8% or less, and even more preferably in both the conductive region 16 and the non-conductive region 17. 7% or less. In addition, the maximum value of the light absorptance of the transparent conductive member 10 having a wavelength of 450 to 800 nm is preferably 15% or less, more preferably 10% or less, in both the conducting region 16 and the non-conducting region 17. More preferably, it is 9% or less. On the other hand, the average reflectance of light having a wavelength of 500 to 700 nm of the transparent conductive member 10 is preferably 20% or less, more preferably 15% or less, in both the conductive region 16 and the non-conductive region 17. More preferably, it is 10% or less. The lower the average absorptance and average reflectance of the transparent conductive member 10, the higher the above-mentioned average transmittance.

The average transmittance, average absorption rate, and average reflectance are preferably the average transmittance, average absorption rate, and average reflectance measured in the usage environment of the transparent conductive member 10. Specifically, when the transparent conductive member 10 is used by being bonded to an organic resin, a layer made of the organic resin may be disposed on the transparent conductive member 10 to measure average transmittance and average reflectance. preferable. On the other hand, when the transparent conductive member 10 is used in the air, it is preferable to measure the average transmittance and the average reflectance in the air. The transmittance and the reflectance are measured with a spectrophotometer by making measurement light incident from an angle inclined by 5 ° with respect to the normal line of the surface of the transparent conductive member 10. The absorptance is calculated by a calculation formula of [100− (transmittance + reflectance)].

Further, when the transparent conductive member 10 has the conductive region 16 and the non-conductive region 17 as shown in FIG. 2, it is preferable that the reflectivity of the conductive region 16 and the reflectivity of the non-conductive region 17 are approximated. Specifically, the difference ΔR between the luminous reflectance of the conductive region 16 and the luminous reflectance of the non-conductive region 17 is preferably 5% or less, more preferably 3% or less, and even more preferably. Is 1% or less, particularly preferably 0.3% or less. On the other hand, the luminous reflectance of the conductive region 16 and the non-conductive region 17 is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less. The luminous reflectance is a Y value measured with a spectrophotometer (U4100; manufactured by Hitachi High-Technologies Corporation).

Further, when the transparent conductive member 10 includes the conductive region 16 and the non-conductive region 17, the a ^* value and the b ^* value in the L ^* a ^* b ^* color system must be within ± 30 in any region. Is preferable, more preferably within ± 5, still more preferably within ± 3.0, and particularly preferably within ± 2.0. If the a ^* value and b ^* value in the L ^* a ^* b ^* color system are within ± 30, both the conductive region 16 and the non-conductive region 17 are observed as colorless and transparent. The a ^* value and b ^* value in the L ^* a ^* b ^* color system are measured with a spectrophotometer.

The surface electrical resistance of the conductive region 16 of the transparent conductive member 10 is 50Ω / sq. Or less, more preferably 30 Ω / sq. It is as follows. The surface electric resistance value of the conduction region 16 is 50Ω / sq. The following transparent conductive member 10 can be applied to a transparent conductive panel for a capacitive touch panel. The surface electrical resistance value of the conduction region 16 is adjusted by the thickness of the metal layer 13 and the like. The surface electrical resistance value of the conduction region 16 is measured in accordance with, for example, JIS K7194, ASTM D257, or the like. It is also measured by a commercially available surface electrical resistivity meter.

<2. Embodiment of Transparent Conductive Member (Second Embodiment)>
Next, a second embodiment of the transparent conductive member will be described. 3 and 4 show a schematic configuration (cross-sectional view) of the transparent conductive member of the second embodiment. FIG. 4 is a modification of the embodiment shown in FIG.

[Basic configuration of transparent conductive member]
The transparent conductive member 20 of the second embodiment shown in FIG. 3 has a configuration in which a first dielectric layer 12, a first antisulfurization layer 18, a metal layer 13, and a second dielectric layer 14 are laminated in this order. is doing. A transparent conductive member 20 is provided on the transparent substrate 11.

Further, the transparent conductive member 20A of the modified example of the second embodiment shown in FIG. 4 includes a first dielectric layer 12, a first sulfidation preventing layer 18, a metal layer 13, a second sulfidation preventing layer 19, and a second dielectric. It has the structure which laminated | stacked the body layer 14 in this order. A transparent conductive member 20 </ b> A is provided on the transparent substrate 11.

In the transparent conductive members 20 and 20A described above, the same configuration as that of the transparent conductive member of the first embodiment described above can be applied except that the first sulfide prevention layer 18 and the second sulfide prevention layer 19 are provided. . For this reason, in the following description, only the structure regarding the 1st sulfidation prevention layer 18 and the 2nd sulfidation prevention layer 19 is explained, and explanation of other composition is omitted.

Also in the transparent conductive members 20 and 20A of the second embodiment, as shown in FIG. 2 described above, the conductive region 16 in which the metal layer 13 is continuously formed and the non-conductive region 17 in which the metal layer 13 is not formed. Thus, a desired conductive layer pattern can be formed. At this time, in the non-conductive region 17, the first sulfidation preventing layer 18 and the second sulfidation preventing layer 19 are also removed together with the first dielectric layer 12, the metal layer 13, and the second dielectric layer 14. It is preferable.

[First antisulfurization layer]
In the transparent conductive members 20 and 20A, the first dielectric layer 12 or the second dielectric layer 14 preferably contains zinc sulfide. Therefore, for example, when the first dielectric layer 12 is a layer containing zinc sulfide, as shown in FIG. 3, the first anti-sulfurization layer 18 is provided between the first dielectric layer 12 and the metal layer 13. It is preferable to form. The first sulfidation preventing layer 18 may be formed also in the non-conductive region of the transparent conductive members 20 and 20A. However, from the viewpoint of making it difficult to visually recognize the pattern including the conductive region 16 and the non-conductive region. It is preferable to form only in.

The first sulfidation preventing layer 18 can be configured as a layer containing metal oxide, inorganic oxide, metal nitride, metal fluoride, or the like, or Zn. The first sulfurization preventing layer 18 may contain only one kind or two or more kinds, but preferably contains a compound containing a zinc metal element. However, when the first dielectric layer 12, the first sulfidation preventing layer 18 and the metal layer 13 are continuously formed, the first sulfidation is performed by a compound capable of reacting with sulfur or adsorbing sulfur. It is preferable that the prevention layer 18 is formed. In the case where the metal oxide is a compound that reacts with sulfur, the reaction product of the metal oxide and sulfur preferably has high visible light permeability.

Metal oxides, inorganic oxides, metal nitrides, and metal fluorides that can be applied to the first antisulfurization layer 18 are described in the description of the first dielectric layer 12 and the second dielectric layer 14, Mention may be made of compounds similar to metal oxides, metal nitrides, and metal fluorides. In particular, Zn, ZnO, IZO (indium oxide / zinc oxide), and GZO (gallium-doped zinc oxide) are preferable.

Here, it is preferable that the thickness of the first sulfidation preventing layer 18 is a thickness capable of protecting the surface of the first dielectric layer 12 from an impact when the metal layer 13 is formed. On the other hand, zinc sulfide that can be included in the first dielectric layer 12 has a high affinity with the metal included in the metal layer 13. Therefore, if the thickness of the first sulfidation prevention layer 18 is very thin and a part of the first dielectric layer 12 is exposed, the metal layer 13 grows around the exposed part, and the metal layer 13 Tends to be dense. That is, the first sulfidation preventing layer 18 is preferably relatively thin, preferably in the range of 0.1 to 15 nm, more preferably in the range of 0.5 to 10 nm, and even more preferably 1 to 5 nm. Is within the range. The thickness of the first sulfurization preventive layer 18 can be measured using an ellipsometer.

The first antisulfurization layer 18 can be formed by a general vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, etc. It is preferable to do.

When the first antisulfurization layer 18 is a layer patterned into a desired shape, the patterning method is not particularly limited. The first sulfidation preventing layer 18 may be a layer formed in a pattern by a vapor phase forming method by placing a mask having a desired pattern on the surface to be formed, and patterned by a known etching method, for example. It may be a layer formed. Further, the metal film 13, the first dielectric layer 12, and the second dielectric layer 14 may be patterned by laser etching simultaneously.

[Second anti-sulfurization layer]
When the second dielectric layer 14 is a layer containing at least zinc sulfide, as illustrated in FIG. 4, a second antisulfurization layer 19 is provided between the metal layer 13 and the second dielectric layer 14. A formed configuration is preferable.

The second sulfidation preventing layer 19 may be formed also in the non-conductive region of the transparent conductive member 10, but from the viewpoint of making it difficult to visually recognize the pattern composed of the conductive region 16 and the non-conductive region, only the conductive region 16 is provided. Preferably it is formed.

For the second sulfidation preventing layer 19, the same constituent materials and the same construction method as those of the first sulfidation preventing layer 18 can be applied.

The thickness of the second antisulfurization layer 19 is preferably a thickness that can protect the surface of the metal layer 13 from impact during the formation of the second dielectric layer 14. On the other hand, since the metal contained in the metal layer 13 and zinc sulfide contained in the second dielectric layer 14 have high affinity, the thickness of the second antisulfurization layer 19 is very thin, and a part of the metal layer 13 is present. If even a slight amount is exposed, the adhesion between the metal layer 13 or the second antisulfurization layer 19 and the second dielectric layer 14 is likely to increase. Accordingly, the specific thickness of the second antisulfurization layer 19 is preferably 0.1 to 10 nm, more preferably 0.5 to 5 nm, and further preferably 1 to 3 nm. The thickness of the second sulfurization preventing layer 19 is measured with an ellipsometer.

<3. Production Method of Transparent Conductive Member (Third Embodiment)>
Next, the manufacturing method of the transparent conductive member of the above-mentioned embodiment is demonstrated.
The transparent conductive member can be produced using a general vapor deposition method such as a known vacuum deposition method, sputtering method, ion plating method, plasma CVD method, and thermal CVD method. Moreover, it can also produce using general coating liquid phase methods, such as a gravure coat and a die coat.

From the viewpoint of increasing the refractive index (density) of the first dielectric layer 12, the first dielectric layer 12 is preferably a layer formed by an electron beam evaporation method or a sputtering method.

In the sputtering method, since the material collides with the deposition target at high speed during film formation, a dense and smooth film is easily obtained, and the light transmittance of the metal layer 13 is likely to be increased. Further, when the metal layer 13 is a film formed by sputtering, the metal layer 13 is hardly corroded even in a high temperature and low humidity environment. The type of the sputtering method is not particularly limited, and may be an ion beam sputtering method, a magnetron sputtering method, a reactive sputtering method, a bipolar sputtering method, a bias sputtering method, a counter sputtering method, or the like. The metal layer 13 is particularly preferably a film formed by a counter sputtering method. When the metal layer 13 is a film formed by the counter sputtering method, the metal layer 13 becomes dense and the surface smoothness is likely to increase. As a result, the surface electrical resistance of the metal layer 13 becomes lower and the light transmittance is likely to increase.
In the case of the electron beam evaporation method, it is desirable to have assistance such as IAD (ion assist) in order to increase the film density.

The transparent conductive member is preferably produced by a continuous process from the viewpoint of production efficiency.
FIG. 5 shows an example of a manufacturing flow of a transparent conductive member for manufacturing the transparent conductive member in a continuous online process. Below, the manufacturing method of a transparent conductive member using the manufacturing flow shown in FIG. 5 is demonstrated.

In the manufacturing flow shown in FIG. 5, in the transparent conductive member 20 </ b> A according to the modification of the second embodiment shown in FIG. 4, the first dielectric layer 12, the first antisulfurization layer 18, and the metal layer are formed on the transparent substrate 11. 13, the manufacturing method which laminates | stacks the 2nd sulfide prevention layer 19 and the 2nd dielectric material layer 14 in this order is demonstrated.

In the manufacturing flow shown in FIG. 5, in step 1, the first dielectric layer 12 is formed on the transparent substrate 11 in the vacuum deposition chamber 21.
In step 2, the first sulfidation prevention layer 18 is formed on the first dielectric layer 12 in the vacuum deposition chamber 21.
In step 3, the metal layer 13 is formed on the first sulfurization prevention layer 18 in the vacuum deposition chamber 21.
In step 4, a second antisulfurization layer 19 is formed on the metal layer 13 in the vacuum deposition chamber 21.
Then, in step 5, the second dielectric layer 14 is formed on the second sulfurization prevention layer 19 in the vacuum deposition chamber 21.

In step 1, the first resistance heating boat 22 is loaded with a dielectric material, for example, zinc sulfide, and the second resistance heating boat 23 is loaded with an infrared absorbing material, metal oxide, inorganic oxide, metal fluoride, and metal nitridation. At least one compound selected from the product, for example, SiO ₂ is loaded. Then, each target is energized and heated, and the first dielectric layer 12 is formed on the continuously transported transparent substrate 11 by a co-evaporation method.
At this time, by controlling the heating conditions and vapor deposition rate of each resistance heating boat (first resistance heating boat 22, second resistance heating boat 23), zinc sulfide and metal oxide, inorganic oxide, metal fluoride In addition, the ratio of at least one compound selected from metal nitrides and the ratio in the layer can be adjusted.

Next, in step 2, the resistance heating boat 24 is charged with a material for forming the first sulfidation prevention layer 18, for example, ZnO. Then, the first sulfidation prevention layer 18 is formed on the first dielectric layer 12 of the transparent substrate 11 that is continuously conveyed by energization heating under a predetermined condition.

Next, in Step 3, the resistance heating boat 25 is charged with a material for forming the metal layer 13, for example, Ag. And the metal layer 13 is formed on the 1st sulfurization prevention layer 18 of the transparent substrate 11 currently conveyed by carrying out electricity heating on predetermined conditions. At this time, in step 3, it is preferable that the metal layer 13 is formed of silver and the formation rate of the silver layer is 0.3 nm / second or more.
From the viewpoint of realizing higher productivity, the formation rate is more preferably in the range of 0.5 to 30 nm / second, and particularly preferably in the range of 1.0 to 15 nm / second. The vapor deposition method is characterized by extremely high production efficiency compared to the sputtering method.

The formation speed S (nm / second) is obtained as follows.
In Step 3 shown in FIG. 5, a material for forming the metal layer 13 is loaded into the resistance heating boat 25 as an evaporation source. And a monitor glass is arrange | positioned just above this evaporation source, and a metal layer is formed on a monitor glass in the state left still without moving a monitor glass. At this time, the formation time (seconds) required for forming the metal layer and the thickness of the metal layer formed on the monitor glass are measured. The formation speed S (nm / second) is calculated from the measured thickness (nm) / formation time (second) of the genus layer.

Next, in step 4, the resistance heating boat 26 is charged with a material for forming the second sulfidation prevention layer 19, for example, ZnO. Then, the second sulfidation prevention layer 19 is formed on the metal layer 13 of the transparent substrate 11 that is continuously conveyed by energization heating under a predetermined condition.

Finally, in step 5, the first resistance heating boat 27 is loaded with a dielectric material, such as zinc sulfide, and the second resistance heating boat 28 is loaded with metal oxide, inorganic oxide, metal fluoride and metal nitridation. At least one compound selected from the product, for example, SiO ₂ is loaded. Then, each target is energized and heated, and the second dielectric layer 14 is formed on the second sulfidation prevention layer 19 of the transparent substrate 11 continuously conveyed by a co-evaporation method.
At this time, by controlling the heating conditions and vapor deposition rate of each resistance heating boat (first resistance heating boat 27, second resistance heating boat 28), zinc sulfide and metal oxide, inorganic oxide, metal fluoride In addition, the ratio of at least one compound selected from metal nitrides and the ratio in the layer can be adjusted.

Through the steps as described above, the transparent conductive member 20A shown in FIG. 4 can be manufactured.
In the above manufacturing flow, the vapor deposition method using the resistance heating boat has been described as an example, but other vapor deposition methods using an electron beam or the like may be applied, for example.
Moreover, the transparent conductive member of 1st Embodiment shown to FIG.1, 2 and the transparent conductive member of 2nd Embodiment shown in FIG. 3 can also be manufactured similarly to the above-mentioned manufacturing method.

In the step shown in FIG. 5 described above, the pressure P ₃ in the vacuum deposition chamber 21 of the step 3 of forming the metal layer 13, and the pressure P ₁ of the vacuum deposition chamber 21 of the step 1 of forming a first dielectric layer 12, it is preferable to set higher also than the pressure P ₅ in the vacuum deposition chamber 21 of the step 5 of forming a second dielectric layer 14. By setting the pressure P ₃ in step 3 for forming the metal layer 13 higher than the pressures P ₁ and P ₅ for forming the first dielectric layer 12 and the second dielectric layer 14, the pressure in step 1 and step 5 is set. The sulfur component can be prevented from flowing into the step 3 for forming the metal layer 13.

Further, a pressure P _2, the metal layer 13 of the first dielectric layer 12 pressure P ₁ of the vacuum deposition chamber 21 of the step 1 of forming a _vacuum deposition chamber 21 of the step 2 of forming a first anti-sulfuration layer 18 vacuum deposition chamber 21 the pressure P ₃ of the step _3, the pressure P ₄ in the vacuum deposition chamber 21 of the step 4 of forming a second anti-sulfuration layer _19, and a vacuum deposition process 5 forming a second dielectric layer 14 pressure _{P 5} of the chamber 21,
Pressure P ₁ <Pressure P ₂ <Pressure P ₃ > Pressure P ₄ > Pressure P ₅
It is preferable to maintain this relationship. By maintaining this relationship, the inflow of the sulfur component to the step 3 for forming the metal layer 13 can be more efficiently prevented.

Further, in the above-described manufacturing process of the transparent conductive member 20A, it is preferable to include a cooling system that can suppress the temperature rise of the transparent substrate 11 during formation and can control the temperature in the range of −20 to 65 ° C. .

The pressure in each vacuum deposition chamber is preferably in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻³ Pa. In each step, it is preferable to monitor online with a layer thickness monitor so that a desired layer thickness is obtained.

In addition, as a manufacturing method of the 1st dielectric material layer 12 and the 1st dielectric material layer 14, the coating liquid phase method can also be applied besides the above-mentioned vapor-phase film-forming method. As the coating liquid phase method, for example, coating by a wire bar, spin coating, coating by dip coating, or the like can be applied. Moreover, it is possible to apply and form a film using a continuous coating apparatus such as a die coater, a gravure coater, or a comma coater.

[Method for forming transparent conductive member having electrode pattern]
Next, a method for forming a pattern including the conductive region 16 and the non-conductive region 17 as shown in FIG. 2 will be described for the transparent conductive member of each of the embodiments described above.

The patterns of the conductive regions 16 and the non-conductive regions 17 of the transparent conductive members 10, 20, and 20A of the above-described embodiments are formed by irradiating the transparent conductive members 10, 20, and 20A with laser light.
In the transparent conductive members 10, 20, and 20A of the above-described embodiments, the first dielectric layer 12 and the second dielectric layer 14 include an infrared absorbing compound. For this reason, by using a laser having a wavelength corresponding to the infrared absorbing compound contained in the first dielectric layer 12 and the second dielectric layer 14, the first dielectric layer 12 is processed in the same process as the metal layer 13. And the second dielectric layer 14 can be etched.

For this reason, the transparent conductive member 10 having the three-layer structure of the first dielectric layer 12, the metal layer 13, and the second dielectric layer 14 of the first embodiment, and the anti-sulfurization layer 3 of the second embodiment are included. Even in the transparent conductive members 20 and 20A having a laminated structure of more than one layer, all layers including the metal layer 13 can be etched in one step. Therefore, pattern etching of the transparent conductive member can be performed in one step, and the productivity of the transparent conductive member can be increased.

Examples of the laser for forming the pattern of the conductive region 16 and the non-conductive region 17 of the transparent conductive members 10, 20, and 20A include a CO ₂ laser, a YVO laser, a Ne-YAG laser, and an Nd-YVO4 laser. In particular, it is preferable to use the fundamental wave (1064 nm) of a Ne-YAG laser because a high-power and stable laser can be obtained at low cost.

<4. Electronic device>
[Application fields of transparent conductive members]
The transparent conductive member having the above configuration includes various displays such as a liquid crystal method, a plasma method, an organic electroluminescence method, a field emission method, a touch panel, a mobile phone, electronic paper, various solar cells, various electroluminescence dimming elements, and the like. It can be preferably applied to substrates of electronic devices and optoelectronic devices.

When the transparent conductive member is applied to various electronic devices, the surface of the transparent conductive member, for example, when the transparent conductive member is provided on the transparent substrate, the back side of the transparent substrate (the transparent conductive member is formed). In the case where no transparent substrate is provided, the exposed surface of the first dielectric layer may be bonded to another member via an adhesive layer or the like.
In this case, as described above, it is preferable that the admittance coordinates of the adhesive layer and the equivalent admittance coordinates on the surface of the transparent conductive member bonded together by the adhesive layer are approximated. Thereby, reflection at the interface between the transparent conductive member and the adhesive layer is suppressed.
On the other hand, when used in a configuration in which the surface of the transparent conductive member is in contact with air, it is preferable that the admittance coordinates of the air and the admittance coordinates of the surface of the transparent conductive member approximate each other. Thereby, reflection of light at the interface between the transparent conductive member and air is suppressed.

Hereinafter, an example in which a transparent conductive member is applied to a touch panel will be described as an example of an electronic device to which the transparent conductive member of each embodiment described above is applied. FIG. 6 shows an example of the configuration of a touch panel including a transparent conductive member having an electrode pattern.

The touch panel 30 shown in FIG. 6 is a projected capacitive touch panel. The touch panel 30 includes a first transparent conductive member 33 patterned on one main surface of the first transparent substrate 31 and a second transparent conductive pattern formed on one main surface of the second transparent substrate 32. The members 34 are arranged in this order. The upper portions of the second transparent substrate 32 and the second transparent conductive member 34 are covered with the front plate 35.
Each of the first transparent conductive member 33 and the second transparent conductive member 34 has a desired metal layer pattern according to the conductive region and the non-conductive region shown in the first and second embodiments described above. A conductive member can be applied.
Thus, a touch panel can be comprised by laminating | stacking the transparent conductive member formed in the desired pattern via the transparent substrate.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented. Further, in the following description, reference numerals corresponding to the respective configurations shown in FIGS. 2 and 5 are described in parentheses after the constituent requirements of each sample.

<Preparation of transparent conductive member>
Each transparent conductive member of Samples 101 to 121 was produced. Hereinafter, the configuration of each transparent conductive member of Samples 101 to 121 and the manufacturing procedure will be described. Table 1 shows the configuration of the transparent conductive members of Samples 101 to 121 and the evaluation of the transparent conductive members of Samples 101 to 121.

[Preparation of transparent conductive member of sample 101]
As a transparent substrate (11), a polyethylene terephthalate (abbreviation: CHC-PET, manufactured by Kimoto Co.) film on which a double-sided hard coat was formed was prepared. Then, on this CHC-PET film, the first dielectric layer (12) (ZnS-ITO) / metal layer (13) (Ag) / second dielectric layer (14) (by a vapor deposition method according to the following method) ZnS-ITO) were laminated in this order. Then, each formed layer was patterned by the following method, and a transparent conductive member of sample 101 having the same pattern as the wiring shown in FIG.
The thickness of each layer is J. A. Woollam Co. Inc. The measurement was made with a VB-250 VASE ellipsometer manufactured by the manufacturer.

(Formation of first dielectric layer (ZnS-ITO))
As a vacuum deposition apparatus, a BMC-800T deposition apparatus manufactured by SYNCHRON Co., Ltd. was used. ZnS was loaded on the first resistance heating boat (22) made of molybdenum, and ITO was loaded on the second resistance heating boat (23) made of molybdenum. . Then, after reducing the vacuum tank to 1 × 10 ⁻⁴ Pa, the first resistance heating boat (22) and the second resistance heating boat (23) are energized and heated, and the current heating conditions of both resistance heating boats are appropriately set. It was adjusted and co-deposited on the CHC-PET film under the condition that the volume ratio of ZnS and ITO was 99: 1, and the formation rate was 0.3 nm / second and the formation time was 120 seconds. As a result, a first dielectric layer (12) having a layer thickness of 36 nm was formed.
As a result of measurement using X-ray photoelectron spectroscopy (XPS), it was confirmed that the volume ratio of ZnS to ITO in the first dielectric layer was 99: 1.

(Formation of metal layer (Ag))
Next, the CHC-PET film on which the first dielectric layer (12) is formed is fixed to a vacuum vapor deposition apparatus similar to the above, Ag is loaded into a resistance heating boat (25) made of molybdenum, and the vacuum chamber is set to 1 The pressure was reduced to ^10-4 Pa. Then, the resistance heating boat (25) was energized and heated, and was vacuum-deposited on the first dielectric layer under the condition that the formation time was 6 seconds, thereby forming a metal layer (13) having a layer thickness of 7.7 nm. The formation speed at this time was 2.7 nm / second as a result of measurement by the following method.

In step 3 shown in FIG. 5, the formation speed is such that Ag is loaded into a resistance heating boat (25) as an evaporation source, a monitor glass is disposed immediately above the evaporation source, and the monitor glass is not fixed and moved. A metal layer was formed. The formation time required for forming the thin film was 2.85 seconds, and the thickness of the metal layer formed on the monitor glass was 7.7 nm. From the above measurement results, the formation speed S (nm / second) is 2.7 nm from the thickness of the metal layer (nm) / formation time (seconds) = 7.7 (nm) /2.85 (seconds). / Second).

(Formation of second dielectric layer (ZnS-ITO))
Next, the CHC-PET film formed up to the metal layer (13) is fixed to a vacuum vapor deposition apparatus similar to the above, and ZnS is put on the first resistance heating boat (27) made of molybdenum, and the second made of molybdenum. A resistance heating boat (28) was charged with ITO. Then, after reducing the vacuum tank to 1 × 10 ⁻⁴ Pa, the first resistance heating boat (27) and the second resistance heating boat (28) are energized and heated, and the current heating conditions of both resistance heating boats are appropriately set. The second dielectric layer having a layer thickness of 44 nm is prepared by co-evaporation under the conditions that the volume ratio of ZnS and ITO is 99: 1 and the formation speed is 0.37 nm / second and the formation time is 120 seconds. (14) was formed.

(Patterning of transparent conductive member)
Next, laser etching is performed on the formed first dielectric layer (12), metal layer (13), and second dielectric layer (14), and the non-conductive region (17) where the transparent substrate (11) is exposed. ), And a conductive region (16) in which the first dielectric layer (12), the metal layer (13), and the second dielectric layer (14) remained were formed.
The etching conditions at this time were as follows: laser light was irradiated with a laser light wavelength of 1064 nm, a laser output of 5 W, a laser diameter of 60 μm, and a frequency of 30 kHz, and the transport speed of the transparent substrate (11) was 500 mm / second.
The width of the line-shaped non-conducting region (17) was 16 μm.
The transparent conductive member of Sample 101 was produced through the above steps.

[Preparation of transparent conductive members of samples 102 to 104]
The above-described sample 101 was transparent except that the ratio of ITO (infrared absorbing compound) contained in the first dielectric layer (12) and the second dielectric layer (14) was changed as shown in Table 1. Transparent conductive members of Samples 102 to 104 were produced using the same method as the production of the conductive members.

[Preparation of transparent conductive member of sample 105]
In the step of producing the first dielectric layer (12) and the second dielectric layer (14), the volume ratio of ZnS and SiO ₂ is 99: 1 in the first resistance heating boat (22, 27). The second resistance heating boat (23, 28) was charged with ITO, and the formation rate was 4.3 nm / min under the condition that the volume ratio of ZnS—SiO ₂ and ITO was 99: 1. Second, formation time was 10 seconds. Otherwise, the first dielectric layer (12) (ZnS—SiO ₂ —ITO) / metal layer (13) (Ag) / second dielectric layer (14 ) A transparent conductive member of Sample 105 having a layer structure of (ZnS—SiO ₂ —ITO) was prepared.

[Preparation of transparent conductive members of samples 106 and 107]
Except for changing the ratio of ITO contained in the first dielectric layer (12) and the second dielectric layer (14) as shown in Table 1, it is the same as the production of the transparent conductive member of the sample 105 described above. Using the method, transparent conductive members of Samples 106 and 107 were manufactured.

[Preparation of transparent conductive member of sample 108]
Sample 108 was prepared in the same manner as in the preparation of the transparent conductive member of Sample 102 described above, except that ZnS constituting the first dielectric layer (12) and the second dielectric layer (14) was changed to GZO. A transparent conductive member was prepared.

[Production of transparent conductive member of sample 109]
Sample 109 was prepared in the same manner as in the preparation of the transparent conductive member of Sample 102 described above, except that ZnS constituting the first dielectric layer (12) and the second dielectric layer (14) was changed to ZnO. A transparent conductive member was prepared.

[Preparation of transparent conductive member of sample 110]
In the production of the transparent conductive member of the sample 101, the production of the first dielectric layer (12) and the second dielectric layer (14) was changed to the following method.
As a first dielectric layer (12) on a CHC-PET film, ITO fine particles (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.) are mixed with PC200 (titanium oxide film forming agent, Matsumoto Fine Chemical) so as to become 1%, and dried film The coating was formed to a thickness of 30 nm and dried in a drying oven at 100 ° C. for 2 minutes.
Further, 3 nm of ZnS-ITO was produced on the ITO-containing titanium oxide layer by the same method as that for the transparent conductive member of Sample 101.
Thus, a first dielectric layer (12) composed of an ITO-containing titanium oxide layer and ZnS-ITO was produced.

Next, after forming the metal layer (13) by the same method as that of the transparent conductive member of the sample 101, the first dielectric layer (excluding that the PC200 mixed with 1% of ITO fine particles was formed to 40 nm was formed. A second dielectric layer (14) composed of an ITO-containing titanium oxide layer and ZnS-ITO was produced in the same manner as in 12).

[Preparation of transparent conductive member of samples 111 and 112]
Except for changing the concentration of ITO contained in the first dielectric layer (12) and the second dielectric layer (14) as described in Table 1, it is the same as the transparent conductive member of the sample 110 described above. The transparent conductive members of Samples 111 and 112 were produced by the method described above.

[Preparation of transparent conductive member of sample 113]
The material used to fabricate the first dielectric layer (12) and the second dielectric layer (14) was changed from PC200 to XJA-0291C (titanium oxide particle-dispersed UV curable resin composition, Pernox Corporation). A transparent conductive member of Sample 113 was prepared in the same manner as the transparent conductive member of Sample 111 described above, except that after drying, ultraviolet light having an illuminance of 150 mW and a light amount of 100 mJ was irradiated for 5 seconds.

[Preparation of transparent conductive member of sample 114]
The material used for the production of the first dielectric layer (12) and the second dielectric layer (14) was changed from PC200 to XJA-0283 (zirconia oxide particle-dispersed UV curable resin composition, Pernox Corporation). Except for the above, a transparent conductive member of Sample 114 was produced in the same manner as the transparent conductive member of Sample 113 described above.

[Preparation of transparent conductive member of sample 115]
Sample 115 was prepared in the same manner as in the preparation of the transparent conductive member of Sample 102 described above, except that ITO contained in the first dielectric layer (12) and the second dielectric layer (14) was changed to ATO. A transparent conductive member was prepared.

[Preparation of transparent conductive member of sample 116]
Sample 116 was prepared in the same manner as in the preparation of the transparent conductive member of Sample 106 described above except that ITO contained in the first dielectric layer (12) and the second dielectric layer (14) was changed to ATO. A transparent conductive member was prepared.

[Preparation of transparent conductive member of sample 117]
Sample 117 is manufactured in the same manner as in the production of the transparent conductive member of Sample 111 described above, except that ITO contained in the first dielectric layer (12) and the second dielectric layer (14) is changed to ATO. A transparent conductive member was prepared.

[Preparation of transparent conductive member of sample 118]
The ITO contained in the first dielectric layer (12) and the second dielectric layer (14) was changed to TX-EX-902K (manufactured by Nippon Shokubai Co., Ltd.), and the content of TX-EX-902K was 5 The transparent conductive member of Sample 118 was produced by the same method as the production of the transparent conductive member of Sample 110 described above except that the percentage was changed to%.

[Production of transparent conductive member of sample 119]
The first dielectric layer (12) (ZnS-ITO) / metal layer (13) (Ag) / second dielectric layer (14) on the transparent substrate (11) (CHC-PET film) by the following sputtering method (ZnS-ITO) was laminated in order.

(Formation of first dielectric layer (ZnS))
Using a magnetron sputtering apparatus manufactured by Osaka Vacuum Co., Ar: 20 sccm, O ₂ : 0 sccm, sputtering pressure 0.1 Pa, room temperature, target side power 150 W, formation rate 0.3. Under the condition of nm / second, a ZnS target and an ITO target were juxtaposed in a volume ratio of 85:15 and RF sputtering was performed to form a first dielectric layer (12) having a layer thickness of 28 nm. The target-substrate distance was 90 mm.

(Formation of metal layer (Ag))
Using a counter sputtering machine manufactured by FTS Corporation, Ag was counter sputtered under the conditions of Ar: 20 sccm, sputtering pressure 0.5 Pa, room temperature, target side power 150 W, formation rate 1.4 nm / s, and the layer thickness was A 7.3 nm metal layer (13) was formed. The target-substrate distance was 90 mm.

(Second dielectric layer (ZnS))
Using Anelva L-430S-FHS, ZnS target and ITO under conditions of Ar: 20 sccm, O ₂ : 5 sccm, sputtering pressure 0.3 Pa, room temperature, target side power 150 W, formation rate 0.2 nm / s RF sputtering was performed with the targets arranged in parallel at a volume ratio of 85:15 to form a second dielectric layer (14) having a layer thickness of 36 nm. The target-substrate distance was 86 mm.

(Patterning of transparent conductive member)
Next, laser etching was performed on the first dielectric layer (12), the metal layer (13), and the second dielectric layer (14) by the same method as that of the sample 101 described above.
A transparent conductive member of Sample 119 was produced through the above steps.

[Preparation of transparent conductive member of sample 120]
The first dielectric layer (12) and the second dielectric layer (14) are made of only ZnS and do not contain ITO, except that the first dielectric layer (12) ), A metal layer (13), and a second dielectric layer (14).
Then, the formed first dielectric layer (12), metal layer (13), and second dielectric layer (14) were patterned by the following method.

(Patterning of transparent conductive member)
First, before forming the resist layer, the first dielectric layer (12), the metal layer (13), and the second dielectric layer (14) were subjected to ultrasonic cleaning treatment. An ultrasonic cleaning treatment was performed at 25 ° C. for 4 minutes using a detergent “Clean 30-30 (10%)” manufactured by Kao Corporation as a cleaning solution. Next, after washing with pure water at 25 ° C. five times, ultrasonic washing with pure water at 25 ° C. was performed twice for 4 minutes. Finally, water was scattered with a spin coater and then dried in an oven.

Next, OFPR-800LB manufactured by Tokyo Ohka Kogyo Co., Ltd. is applied as a resist on the cleaned first dielectric layer (12), metal layer (13), and second dielectric layer (14) by spin coating. Then, application and drying were performed at 2000 rpm for 30 seconds to form a resist layer having a thickness of 1 μm.

Next, ultraviolet rays were irradiated through a mask under conditions of 60 mJ, and developed using a developer for positive photoresist “Tokuso SD-1” (tetramethylammonium hydroxide) manufactured by Tokuyama Corporation as a developer. .

Next, “ITO series” manufactured by Kanto Chemical Co., Ltd. is used as an etchant, and the non-conductive region (17) where the transparent substrate is exposed, the first dielectric layer (12), the metal layer (13), and the second An electrode pattern composed of a current-carrying region (16) in which the dielectric layer (14) remained was formed.
The width of the line-shaped non-conducting region (17) was 16 μm.
Finally, the remaining resist layer was peeled off using acetone to form an electrode pattern having wiring.

[Preparation of transparent conductive member of sample 121]
The transparent conductive member of the sample 121 was formed in the same manner as the sample 101 except that the first dielectric layer (12) and the second dielectric layer (14) were formed only of ZnS and did not contain ITO. Produced.

[Evaluation of transparent conductive member]
The absorptance at a laser beam wavelength of 1064 nm was measured for each of the transparent conductive members of Samples 101 to 121 produced as described above.
Further, the following characteristic values were measured and evaluated before (before etching) and after patterning (after etching) the transparent conductive members of Samples 101 to 121.
The evaluation results of each sample are shown in Table 1.

(Measurement of sheet resistance)
A resistivity meter “Loresta EP MCP-2560” manufactured by Mitsubishi Chemical Analytech Co., Ltd. was brought into contact with the transparent conductive member of each sample, and the sheet resistance value (Ω / sq.) Of the conductive region (16) was measured.

(Measurement of average transmittance and absorptance of laser beam wavelength 1064 nm)
About the transparent conductive member of each sample, the average transmittance | permeability was measured in accordance with the following method.
Matching oil (refractive index = 1.515 manufactured by Nikon Corporation) was applied to the surface of the transparent conductive member of each sample on the second dielectric layer (14) side. Then, the transparent conductive member and a non-alkali glass substrate (EAGLE XG (thickness 7 mm × length 30 mm × width 30 mm) manufactured by Corning) were bonded together, and the average in the wavelength range of 400 to 1200 nm from the alkali-free glass substrate side. The transmittance (%) was measured.
At this time, measurement light (for example, light having a wavelength of 450 nm to 1200 nm) is incident on the conduction region from an angle inclined by 5 ° with respect to the normal line of the surface of the alkali-free glass substrate. The light transmittance was measured at U4100.
Furthermore, from the measured value at the wavelength 1064, the absorptance (%) of the laser light wavelength 1064 nm of each sample was measured.

(Measure haze)
About the transparent conductive member of each sample, HDH was measured using NDH7000 (made by Nippon Denshoku Industries Co., Ltd.) with the second dielectric layer (14) facing the light incident side.

 

As is apparent from the results shown in Table 1, the transparent conductive members of Samples 101 to 119 having infrared absorbing compounds in the first dielectric layer and the second dielectric layer have absorption in the 1064 nm laser. Yes. For this reason, it can be seen that desired etching is possible with the laser, and the transmittance, resistance value, and haze are good.

On the other hand, the transparent conductive members of the sample 120 and the sample 121 that do not have the infrared absorbing compound in the first dielectric layer and the second dielectric layer do not have absorption in the 1064 nm laser. For this reason, the transparent conductive member of the sample 121 was not satisfactorily laser-etched and could not be measured for each evaluation after the etching.
Further, even in the sample 120 subjected to wet etching, the etching was not performed well, and each evaluation after the etching could not be measured.

The present invention is not limited to the configuration described in the above embodiment, and various modifications and changes can be made without departing from the configuration of the present invention.

10, 20, 20A ... transparent conductive member, 11 ... transparent substrate, 12 ... first dielectric layer, 13 ... metal layer, 14 ... second dielectric layer, 15 ... Opening portion, 16 ... conduction region, 17 ... non-conduction region, 18 ... first sulfidation prevention layer, 19 ... second sulfidation prevention layer, 21 ... vacuum evaporation chamber, 22, 27 ..First resistance heating boat, 23, 28... Second resistance heating boat, 24, 25, 26... Resistance heating boat, 30... Touch panel, 31. ... 2nd transparent substrate, 33 ... 1st transparent conductive member, 34 ... 2nd transparent conductive member, 35 ... Front plate

Claims (9)

1. A first dielectric layer;
   A second dielectric layer;
   A metal layer formed between the first dielectric layer and the second dielectric layer,
   An infrared ray absorbing compound is contained in the first dielectric layer and the second dielectric layer. A transparent conductive member.
2. The transparent conductive member according to claim 1, wherein the infrared absorbing compound contains at least one of indium-doped tin oxide and antimony-doped tin oxide.
3. The transparent conductive member according to claim 1 or 2, wherein the concentration of the infrared absorbing compound is 1% by mass or more and 30% by mass or less.
4. The conductive region in which the first dielectric layer, the metal layer, and the second dielectric layer are formed, and the first dielectric layer, the metal layer, and the second dielectric layer are removed. The transparent conductive member according to claim 1, further comprising a non-conductive region.
5. The transparent conductive member according to claim 4, wherein the non-conductive region is formed by laser etching.
6. The transparent conductive member according to claim 1, further comprising an anti-sulfurization layer between the first dielectric layer, the second dielectric layer, and the metal layer.
7. Forming a first dielectric layer containing an infrared absorbing compound;
   Forming a metal layer on the first dielectric layer;
   Forming a second dielectric layer containing an infrared absorbing compound on the metal layer. A method for producing a transparent conductive member.
8. The method for producing a transparent conductive member according to claim 7, further comprising a step of forming a non-conductive region by removing the first dielectric layer, the metal layer, and the second dielectric layer.
9. The method for producing a transparent conductive member according to claim 8, wherein the step of forming the non-conductive region is performed by laser etching.

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