WO2015119240A1 - Stratifié conducteur transparent, procédé de fabrication de stratifié conducteur transparent, et dispositif électronique formé à l'aide du stratifié conducteur transparent - Google Patents

Stratifié conducteur transparent, procédé de fabrication de stratifié conducteur transparent, et dispositif électronique formé à l'aide du stratifié conducteur transparent Download PDF

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WO2015119240A1
WO2015119240A1 PCT/JP2015/053364 JP2015053364W WO2015119240A1 WO 2015119240 A1 WO2015119240 A1 WO 2015119240A1 JP 2015053364 W JP2015053364 W JP 2015053364W WO 2015119240 A1 WO2015119240 A1 WO 2015119240A1
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zinc oxide
oxide film
transparent conductive
film
gallium
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PCT/JP2015/053364
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Japanese (ja)
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務 原
智史 永縄
公市 永元
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リンテック株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8051—Anodes
    • H10K59/80517—Multilayers, e.g. transparent multilayers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates

Definitions

  • the present invention relates to a transparent conductive laminate, a method for producing a transparent conductive laminate, and an electronic device using the transparent conductive laminate, and in particular, a transparent conductive laminate excellent in wet heat characteristics, such a transparent
  • the present invention relates to a method for manufacturing a conductive laminate, and an electronic device using such a transparent conductive laminate.
  • a transparent conductive laminate using tin-doped indium oxide as a material for forming a transparent conductive layer has been widely used.
  • a transparent conductive laminate using zinc oxide with excellent transparency and surface smoothness has been proposed as an alternative to a transparent conductive layer using tin-doped indium oxide containing a large amount of indium, which is an expensive and rare metal.
  • a transparent conductive film is proposed in which an Al 2 O 3 thin film is formed on an organic polymer film substrate, and a GZO thin film of ZnO doped with Ga is formed thereon. (For example, refer to Patent Document 1).
  • a low-resistivity transparent conductor which has a zinc oxide as a main component and a dopant whose concentration can be easily controlled. That is, a transparent conductor composed of zinc oxide, indium oxide, and gallium oxide, and a low-resistivity transparent conductor in which the element concentrations of indium and gallium are each within a predetermined range has been proposed (for example, Patent Documents). 2).
  • a transparent conductive zinc oxide film doped with a specific element has been proposed for the purpose of obtaining excellent moisture and heat resistance characteristics even at an extremely thin film level. That is, a first element composed of Ga and / or Al and a second element composed of at least one selected from the group consisting of In, Bi, Se, Ce, Cu, Er, and Eu are added to zinc oxide.
  • a conductive zinc oxide film has been proposed (for example, Patent Document 3).
  • an ion plating target for transparent conductive zinc oxide thin film excellent in moist heat resistance and obtained therefrom is obtained.
  • a transparent conductive zinc oxide thin film has been proposed (for example, Patent Document 4). More specifically, it is an ion plating target made of a sintered body in which gallium and indium are contained in zinc oxide, and the mass ratio of In / Ga in the obtained transparent conductive zinc oxide thin film is 0. .01 to less than 0.6.
  • Patent Document 5 a conductive film having a multi-layer structure having a plurality of ZnO conductive films mainly composed of a zinc oxide film (ZnO), which has practical moisture resistance and the like, and a manufacturing method thereof Has been proposed (for example, Patent Document 5).
  • ZnO zinc oxide film
  • a conductive film having a multi-layer structure including two or more conductive film layers grown on a substrate by doping a group III element oxide into zinc oxide, the surface of the substrate, A first ZnO conductive film layer containing ZnO as a main component, which is formed so as to be in contact with or not containing a group III element oxide as a dopant, and a first ZnO conductive film layer formed on the first conductive film layer;
  • the conductive film layer is a conductive film comprising a transparent second ZnO conductive film layer containing a different group III element oxide as a dopant.
  • the crystallinity is high and the moisture resistance is excellent on a first conductive film layer (for example, a GZO film) of 5 to 50 nm.
  • a second conductive film for example, an AZO film
  • the film is heated and formed at a high temperature of 200 ° C. or higher to a value exceeding 350 nm.
  • the transparent conductive film disclosed in Patent Document 1 requires an Al 2 O 3 thin film as an undercoat layer
  • the zinc oxide film doped only with gallium still has insufficient moisture and heat resistance characteristics. There was a problem.
  • the low resistivity transparent conductor disclosed in Patent Document 2 has improved the resistivity, there has been a problem that no consideration has been given to the wet heat characteristics.
  • the transparent conductive zinc oxide film disclosed in Patent Document 3 has some wet heat characteristics, the film forming conditions are relatively severe, and the film thickness must be 140 nm or less.
  • the transparent conductive zinc oxide film disclosed in Patent Document 4 cannot be formed by a general-purpose sputtering apparatus, and is characterized by being formed by expensive ion plating. There was a problem that it became an economic disadvantage.
  • the conductive film having a multi-layer structure disclosed in Patent Document 5 limits the film thickness of the first conductive film layer that may not contain a dopant to a range of 5 to 50 nm, and the second conductive film. There are structural and manufacturing constraints that the film layer must be formed with a considerable film thickness (for example, 360 nm). Further, in the conductive film formed on the glass substrate (see Example 1, FIG. 1), there was a problem that the resistance change rate was still as large as about 1.5% after 200 hours after the moisture resistance test. Furthermore, in order to form a second conductive film having high crystallinity and excellent moisture resistance on the first conductive film layer, it is heated and formed at a high temperature of 200 ° C. or higher. There has been a problem that the types of substrates are excessively limited.
  • the present inventors have found that the transparent conductive layer is formed of a multilayer structure of the first zinc oxide film and the second zinc oxide film, and the first zinc oxide It has been found that the film and the second zinc oxide film have a predetermined composition and a predetermined film thickness, respectively, so that even if the total thickness is relatively thin, the wet heat characteristics are excellent, and the present invention has been completed. is there. That is, the present invention aims to provide a transparent conductive laminate excellent in wet heat characteristics, a method for producing such a transparent conductive laminate, and an electronic device using such a transparent conductive laminate. And
  • a transparent conductive laminate is formed by forming a transparent conductive layer on at least one side of a substrate, and the transparent conductive layer is on the substrate side.
  • the first zinc oxide film and the second zinc oxide film are sequentially formed along the film thickness direction from 1 to 3, and the total thickness of the transparent conductive layer is 350 nm or less, and the first zinc oxide film Is a zinc oxide film that does not contain indium as a dopant, contains gallium, and has a thickness of more than 50 nm, and the second zinc oxide film contains indium and gallium as dopants.
  • the laminated body can be provided and the above-described problems can be solved.
  • a transparent conductive laminate having a transparent conductive layer having a predetermined film thickness or less a first zinc oxide film having a predetermined film thickness or more, which does not contain a specific dopant and is doped with another element, and a plurality of specific elements Since the second zinc oxide film doped with is sequentially laminated to form a multilayer structure, the wet heat characteristics can be remarkably improved while maintaining low resistance while being a thin film.
  • the second zinc oxide film (sometimes referred to as an In-GZO film) is subjected to XPS analysis in the film thickness direction as shown in FIG. 2, or as shown in FIG.
  • first region and second region having a non-uniform concentration distribution with respect to zinc amount, gallium amount, oxygen amount, and indium amount measured by SIMS (Secondary Ion Mass Spectrometry) analysis are included.
  • SIMS Single Ion Mass Spectrometry
  • the present invention treats the zinc oxide film as a single layer even in such a case (the same applies hereinafter).
  • a transparent conductive laminate comprising a transparent conductive layer formed on at least one surface of a substrate, the transparent conductive layer The layer is formed by sequentially forming the second zinc oxide film and the first zinc oxide film along the film thickness direction from the substrate side, and the total thickness of the transparent conductive layer is 350 nm or less,
  • the zinc oxide film 1 is a zinc oxide film that does not contain indium as a dopant and also contains gallium, and the second zinc oxide film contains indium and gallium as dopants, and the film thickness exceeds 50 nm.
  • a transparent conductive laminate characterized by the above can be provided to solve the above-mentioned problems.
  • a second zinc oxide film doped with a specific element on a substrate and a first zinc oxide film having a predetermined film thickness that does not contain the specific dopant and is doped with another element are sequentially formed. Since it is laminated and has a multilayer structure with a total thickness of a predetermined thickness or less, it effectively prevents moisture and the like from entering the interface between the second zinc oxide film and the base material. Even in the case of a thin film, the wet heat characteristics of the transparent conductive layer can be remarkably improved.
  • the second zinc oxide film is composed of the total amount of zinc, gallium, oxygen, and indium by XPS elemental analysis ( 100 atom%), the amount of indium is preferably set to a value in the range of 0.01 to 25 atom%.
  • the initial specific resistance in the transparent conductive layer was set to ⁇ 0 and stored for 500 hours at 60 ° C. and 95% relative humidity.
  • the specific resistance after the [rho 500 it is preferable that 1.3 the following values the ratio represented by ⁇ 500 / ⁇ 0.
  • the total thickness of the transparent conductive layer comprising the first zinc oxide film and the second zinc oxide film is a value within the range of 70 to 350 nm. It is preferable that By comprising in this way, even if it is a thin film of predetermined thickness, the wet heat characteristic of a transparent conductive layer can be improved significantly.
  • the zinc content, the gallium content, the oxygen content, and the indium content measured by XPS analysis in the film thickness direction in the second zinc oxide film is preferable that the first region and the second region are included as a plurality of regions having a non-uniform concentration distribution.
  • the relative indium amount increases in the film thickness direction from the zinc oxide film toward the substrate.
  • the second zinc oxide film since it includes a plurality of regions (first region and second region) having a non-uniform concentration distribution that subsequently decreases, the second zinc oxide film, and thus the wet heat characteristics of the transparent conductive film layer including the second zinc oxide film Can be significantly improved.
  • the substrate is made of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, cycloolefin copolymer, cycloolefin polymer, polyethersulfone, and polyimide.
  • Another aspect relating to the present invention is an electronic device characterized by using any of the transparent conductive laminates described above as a transparent electrode.
  • long-term stability of an electronic device can be suitably achieved by using a transparent conductive laminate excellent in wet heat characteristics for a transparent electrode.
  • Still another aspect of the present invention is a method for producing a transparent conductive laminate comprising a transparent conductive layer having a total thickness of 350 nm or less on at least one side of a substrate,
  • the transparent conductive layer is formed by sequentially forming a first zinc oxide film and a second zinc oxide film along the film thickness direction from the substrate side, and includes the following steps (1) to (3): It is a manufacturing method of the transparent conductive laminated body characterized by the above-mentioned.
  • Step of preparing a base material, a first sintered body for zinc oxide film, and a second sintered body for zinc oxide film (2) On the base material, using a sputtering method, A step of forming a first zinc oxide film containing no indium as a dopant and containing gallium and having a thickness exceeding 50 nm from the sintered body for zinc oxide film of (1) (3) First zinc oxide film A step of forming a second zinc oxide film containing indium and gallium as dopants from the second sintered body for zinc oxide film using a sputtering method, that is, the present invention (first invention) By forming a transparent conductive layer having a different composition composition and at least a two-layer structure, a transparent conductive laminate excellent in electrical characteristics and wet heat characteristics can be stably produced even with a thin film having a predetermined thickness or less. be able to.
  • the present invention after the step (3), as the step (4), another first of the same composition as the first zinc oxide film is formed on the surface of the second zinc oxide film. It is preferable to include a step of further stacking the zinc oxide film. That is, regarding the present invention (the first invention), by forming a transparent conductive layer having at least a three-layer structure, a transparent conductive laminate further excellent in wet heat characteristics can be efficiently produced.
  • Still another aspect of the present invention is a method for producing a transparent conductive laminate comprising a transparent conductive layer having a total thickness of 350 nm or less on at least one surface of a substrate,
  • the transparent conductive layer is formed by sequentially forming the second zinc oxide film and the first zinc oxide film along the film thickness direction from the base material side, and the following steps (1 ′) to (3 ′)
  • a transparent conductive layer having at least a two-layer structure a transparent conductive laminate excellent in electrical characteristics and wet heat characteristics can be stably produced even if it is a relatively thin film. Can do.
  • step (4 ′) another surface having the same composition as the second zinc oxide film is formed on the surface of the first zinc oxide film. It is preferable to include a step of further laminating the second ′ zinc oxide film. That is, regarding the present invention (second invention), by forming a transparent conductive layer having at least a three-layer structure, a transparent conductive laminate superior in wet heat characteristics can be efficiently produced.
  • a sintered body having a gallium content of 4.1 to 7.4% by weight is used as the second sintered body for zinc oxide film.
  • a sintered body containing a predetermined amount of gallium not only wet heat characteristics but also electrical characteristics. It is possible to efficiently produce a transparent conductive laminate excellent in thickness.
  • FIGS. 1 (a) to 1 (d) are diagrams for explaining various aspects of a transparent conductive laminate including a transparent conductive layer of the present invention.
  • FIGS. 2A to 2C are diagrams provided for explaining the zinc oxide film (first region and second region) based on XPS measurement.
  • FIG. 3 is a diagram provided for explaining the zinc oxide film (first region and second region) based on SIMS measurement.
  • FIG. 4 is an X-ray diffraction chart of the second zinc oxide film by the In Plane method.
  • FIG. 5 is an X-ray diffraction chart of the second zinc oxide film on the 002 plane according to the Out of Plane method.
  • FIG. 6 is a diagram for explaining the relationship between the film thickness of the second transparent conductive film and the change in specific resistance before and after the environmental test.
  • 1st Embodiment is related with 1st invention, Comprising: It is a transparent conductive laminated body formed by forming a transparent conductive layer in the at least single side
  • the transparent conductive laminate of the first embodiment will be specifically described with reference to the drawings as appropriate.
  • the first zinc oxide film is a zinc oxide film (GZO film) having a predetermined film thickness (d1) that does not contain indium and contains gallium as a dopant. . More specifically, as shown in FIG. 1 (a) or (c), the first zinc oxide film is formed on at least one surface of the base material 12 and does not contain indium and is doped with gallium.
  • the zinc oxide film 16 has a thickness (d1) exceeding 50 nm.
  • zinc oxide is contained as a main component, and in order to improve conductivity, indium is not contained as a dopant and gallium is contained. (Hereinafter sometimes referred to as a GZO film).
  • aluminum, boron, silicon, tin, germanium, antimony, iridium, rhenium, cerium, zirconium, magnesium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, technetium, ruthenium , Rhodium, palladium, silver, lanthanoid, hafnium, tantalum, tungsten, platinum, gold, bismuth, actinoid, scandium and yttrium may be included.
  • the amount of gallium in the first zinc oxide film is a value in the range of 0.1 to 10 atom% with respect to the total amount of zinc, gallium, and oxygen (100 atom%) by XPS elemental analysis measurement. It is preferable to do. This is because the electrical characteristics may be inferior when the amount of gallium falls outside the above range. Therefore, when the first zinc oxide film is a zinc oxide film doped with gallium, the amount of gallium is 0.5 to 8 atoms relative to the total amount of zinc, gallium and oxygen (100 atom%). % Is more preferable, and a value within the range of 1 to 7 atom% is more preferable.
  • the first zinc oxide film does not contain indium.
  • “does not contain indium” specifically refers to the amount of zinc by XPS elemental analysis and gallium in the blending amount of the above-mentioned various additive elements contained in the first zinc oxide film.
  • the amount of indium may be 0 atom% or a value in the range of more than 0 and less than 0.01 atom% with respect to the total amount (100 atom%) of the amount, oxygen amount, and indium amount.
  • each element amount by XPS elemental analysis measurement means the average value of the element amount in each depth measured by the XPS analysis of the depth direction in the whole transparent conductive layer.
  • the film thickness (d1) of the first zinc oxide film is a value exceeding 50 nm. The reason is that when the thickness (d1) of the first zinc oxide film is 50 nm or less, the specific resistance of the first zinc oxide film increases and the specific resistance as the transparent conductive layer may increase. Because there is. On the other hand, if the film thickness (d1) of the first zinc oxide film becomes excessively thick, it takes a long time to form the first zinc oxide film, resulting in a decrease in productivity and a decrease in adhesion to the substrate. However, film warping may occur. Accordingly, the thickness (d1) of the first zinc oxide film is more preferably in the range of 60 to 250 nm, and further preferably in the range of 70 to 150 nm. The film thickness (d1) of the first zinc oxide film can be measured using a spectroscopic ellipsometer, as will be specifically described in Example 1.
  • the initial specific resistance ( ⁇ 0 ) of the first zinc oxide film 16 is preferably set to a value within the range of 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. This is because, when the initial specific resistance of the first transparent conductive layer is less than 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, the film forming conditions may be complicated. On the other hand, when the initial specific resistance of the first transparent conductive layer exceeds 1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, suitable conductivity may not be obtained when the transparent conductive laminate is formed. Because.
  • the initial specific resistance of the first transparent conductive film layer is more preferably set to a value in the range of 3 ⁇ 10 ⁇ 4 to 8 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and 5 ⁇ 10 ⁇ 4 to 5 ⁇ 10. More preferably, the value is within the range of ⁇ 3 ⁇ ⁇ cm.
  • the specific resistance ( ⁇ ) of the first transparent conductive layer can be calculated from the film thickness (d1) of the first transparent conductive layer and the measured surface resistivity (R).
  • the second zinc oxide film is a zinc oxide film (In-GZO film) containing indium and gallium as dopants. More specifically, as shown in FIGS. 1A and 1C, the second zinc oxide film 10 is formed on the first zinc oxide film 16, and indium and gallium are used as dopants. A zinc oxide film comprising the same.
  • the second zinc oxide film is a zinc oxide film containing zinc oxide and doped with indium and gallium
  • the blending amount of various additive elements contained in the transparent conductive layer is measured by XPS elemental analysis.
  • the amount of indium is in the range of 0.01 to 25 atom%
  • the amount of gallium is 0.1 to 10 atom. It is preferable to set the value within the range of%. This is because practical wet heat characteristics and electrical characteristics can be obtained if the amount of indium in the transparent conductive layer is within a predetermined range. Further, regarding the amount of gallium, if the value is out of the above range, the electrical characteristics may be inferior.
  • the amount of zinc, gallium, oxygen, and indium by XPS elemental analysis is measured in the second zinc oxide film.
  • the amount of indium is a value in the range of 0.02 to 8 atom% and the amount of gallium is a value in the range of 0.5 to 10 atom% with respect to the total amount (100 atom%).
  • the amount of indium is a value in the range of 0.1 to 7 atom%, and the amount of gallium is a value in the range of 1 to 10 atom%, and the amount of indium is 0.1 to 6 atom%.
  • each element amount obtained by XPS elemental analysis means an average value of element amounts at each depth in the second region.
  • gallium and indium are selected as the dopant of the second zinc oxide film. That is, the chemical stability of the zinc oxide film can be enhanced by including two or more dopants to be added.
  • gallium and indium in the case of a group 13 element in the periodic table of elements, in the case of assuming that the zinc site has one more valence electron than that of group 12 zinc and a dopant is substituted at the zinc site, aluminum, gallium, and indium This is because each of the first ionization energies is smaller than zinc, and is considered to be effective as a carrier generation source.
  • the first ionization energy is small, it is assumed that the occupied site of zinc which is a dopant is low, and therefore, the Madelung which is an index of bond energy in an ion-bonded ion crystal such as a zinc oxide film.
  • aluminum is -6.44 eV
  • gallium is -13.72 eV
  • indium is -9.73 eV. Therefore, the stability of the zinc oxide film as a dopant is considered to be higher in the order of gallium, indium, and aluminum.
  • the covalent bond radius is 1.25 ⁇ for zinc, 1.18 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ for aluminum, 1.26 ⁇ ⁇ ⁇ ⁇ for gallium, and 1.44 ⁇ ⁇ ⁇ ⁇ ⁇ for indium, while the ionic radius is 0.74 ⁇ ⁇ for zinc and 0 for aluminum. .53 ⁇ , gallium is 0.61 ⁇ , and indium is 0.76 ⁇ .
  • zinc dopant is substituted for the zinc site in the crystal mainly composed of zinc oxide, and considering its structural stability, gallium is most stably substituted from the viewpoint of the covalent bond radius. From the viewpoint of ionic radius, it is presumed that indium is most stably substituted, and therefore these are selected as dopants.
  • the film thickness (d2) of the second zinc oxide film is preferably set to a value of 250 nm or less.
  • the reason for this is that when the thickness (d2) of the second zinc oxide film exceeds 250 nm, the formation of the second zinc oxide film takes an excessive amount of time, resulting in decreased productivity or transparency. This is because the total thickness (d) of the conductive layer is increased, the adhesion to the first zinc oxide film is lowered, and film warping may occur.
  • the film thickness (d2) of the second zinc oxide film becomes excessively thin, not only the specific resistance as the transparent conductive layer increases, but also the wet heat characteristics and the like may remarkably deteriorate.
  • the thickness (d2) of the second zinc oxide film is more preferably in the range of 20 to 230 nm, and still more preferably in the range of 30 to 150 nm.
  • the film thickness (d2) of the second zinc oxide film can also be measured using a spectroscopic ellipsometer, as specifically described in Example 1.
  • the initial specific resistance ( ⁇ 0 ) of the second zinc oxide film 10 exceeds 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm and is 2.1 ⁇ 10 ⁇ 1 ⁇ ⁇ cm or less. It is preferable to do. This is because, when the initial specific resistance of the second zinc oxide film becomes a value of 5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, the film forming conditions may be complicated. On the other hand, if the initial specific resistance of the second zinc oxide film exceeds 1 ⁇ 10 ⁇ 1 ⁇ ⁇ cm, suitable conductivity may not be obtained.
  • the initial specific resistance of the second zinc oxide film is more preferably set to a value in the range of 5.5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm to 1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, more preferably 6 ⁇ 10 ⁇ 4. More preferably, the value is in the range of ⁇ ⁇ cm to 5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • the initial specific resistance ( ⁇ 0 ) of the second zinc oxide film can be calculated from the film thickness (d 2) of the second transparent conductive layer and the measured surface resistivity (R 0 ).
  • the value of the initial specific resistance is about 1 ⁇ 10 ⁇ 3 to 1.2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm when the amount of indium to be doped with the second zinc oxide film is about 2 atom% with respect to the total amount. And it is almost constant.
  • the value of the initial specific resistance also increases gradually and is about 2.5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • the value of the initial specific resistance is about 5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • the initial specific resistance of the second zinc oxide film can be controlled within the above-described preferable range.
  • a zinc oxide film usually has a hexagonal wurtzite crystal structure, and a zinc oxide film doped with gallium (hereinafter referred to as a GZO film) is also a hexagonal wurtzite. It is known that it is a thin film having a type crystal structure and a strong c-axis orientation.
  • the second zinc oxide film is a zinc oxide film containing zinc oxide and doped with gallium and indium (hereinafter sometimes referred to as an In-GZO film). Even if it exists, it turns out that predetermined
  • the characteristic curve E does not contain indium, that is, an X-ray diffraction chart of the GZO film.
  • FIG. 5 shows an X-ray diffraction chart according to the out of plane method on the 002 plane of the second zinc oxide film.
  • the characteristic curves A to E in FIG. 5 have the same contents as the sample corresponding to the X-ray diffraction chart of FIG. Therefore, as understood from the comparison of the X-ray diffraction charts of FIGS. 4 and 5, the second zinc oxide film (In-GZO film) is formed on the first zinc oxide film (GZO film). Since the diffraction peak shows the same diffraction peak as that of the GZO film, it is presumed that the crystal structure is similar. That is, from FIG. 4 and FIG.
  • the In-GZO film that is the second zinc oxide film shows the same diffraction peak as the GZO film that is the first zinc oxide film. Therefore, it is presumed that the second zinc oxide film also has a columnar structure with high c-axis orientation.
  • the initial specific resistance of the second zinc oxide films 10, 10 ′ is ⁇ 0, and the specific resistance after storage for 500 hours at 60 ° C. and 95% relative humidity is ⁇ .
  • the ratio represented by ⁇ 500 / ⁇ 0 is preferably 1.5 or less.
  • the specific resistance after storage for 1000 hours under the conditions of 60 ° C. and 95% relative humidity is ⁇ 1000
  • the ratio represented by ⁇ 1000 / ⁇ 0 may be 2.0 or less. preferable.
  • the specific resistance ( ⁇ 0 , ⁇ 500 , ⁇ 1000 ) of the second zinc oxide film can be measured using a surface resistance measuring device, as specifically described in Example 1.
  • the second zinc oxide film doped with indium or the like has a low increase rate of ⁇ 500 / ⁇ 0 even after 500 hours and maintains a value of 1.3 or less. can do. Therefore, compared to the first zinc oxide film (GZO film), the second zinc oxide film (In-GZO film) has a low rate of change in specific resistance in a humid heat environment over a long period of time. It is understood that the wet heat characteristics are excellent. Therefore, the ratio represented by ⁇ 500 / ⁇ 0 is preferably a value of 1.25 or less, more preferably a value of 1.15 or less, and even more preferably a value of 1.08 or less.
  • the second zinc oxide film is a zinc oxide film containing zinc oxide and doped with gallium and indium.
  • a plurality of regions (first region and second region) having non-uniform concentration distribution with respect to zinc amount, gallium amount, oxygen amount, and indium amount measured by XPS analysis in the depth direction in the film thickness direction toward the substrate ) Is preferably included. More specifically, in the first region, the zinc amount is within a range of 20 to 60 atom% with respect to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement.
  • the gallium content is in the range of 0.1 to 10 atom%
  • the oxygen content is in the range of 22 to 79.89 atom%
  • the indium content is in the range of 0.01 to 8 atom%. It is preferable to set the value of.
  • the zinc amount is set to a value in the range of 35 to 65 atom% with respect to the total amount (100 atom%) of zinc amount, gallium amount, oxygen amount and indium amount by XPS elemental analysis measurement
  • the amount of gallium is set to a value within the range of 0.1 to 10 atom%
  • the amount of oxygen is set to a value within the range of 17 to 64.89 atom%
  • the amount of indium is set to a value within the range of 0.01 to 8 atom%.
  • the value of [In] / [Ga] in the first region is preferably larger than the value of [In] / [Ga] in the second region. That is, with respect to the amount of zinc, the amount of gallium, the amount of oxygen, and the amount of indium in the second zinc oxide film, the first region having a relatively large amount of indium in the film thickness direction from the second zinc oxide film toward the substrate, and When the second region having a relatively small amount of indium is sequentially included, the wet heat characteristics of the second zinc oxide film can be remarkably improved.
  • the interface between the first region and the second region included in the second zinc oxide film is not necessarily clear, and there is a portion where the composition ratio of each region changes continuously or stepwise. It may be.
  • the first region and the second region having different composition ratios may be formed by performing one sputtering process, or may be formed by performing two or more sputtering processes. That is, even in a single sputtering step, a zinc oxide-gallium oxide-indium oxide ternary sintered body is used as a sputtering target, and the blending ratios of the respective components are appropriately adjusted. As shown in FIG.
  • indium in the vicinity of the surface of the zinc oxide film opposite to the substrate side, a relatively large amount of indium (first region) and a relatively small amount of indium inside the zinc oxide film.
  • the region (second region) can be formed continuously. This is because, from the viewpoint of the Madelung energy, gallium is large and stably incorporated into the crystal grains, while indium is presumed to be unstable compared to gallium, and in addition, from the viewpoint of the covalent bond radius. Therefore, it is estimated that indium is larger than zinc and gallium. That is, since indium is expected to have low solubility in zinc oxide, it is presumed that indium that is relatively excessive in maintaining the crystal structure segregates on the surface.
  • the first region and the second region having different composition ratios may be formed by performing the sputtering process two or more times and changing the sputtering conditions, the type of sputtering target, and the like.
  • the base material 12 illustrated in FIG. 1 is not particularly limited as long as it has excellent transparency, and examples thereof include glass, ceramics, and resin films.
  • a resin film as a base material, more specifically, polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, Examples thereof include polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin copolymer, cycloolefin polymer, aromatic polymer, polyurethane polymer, and the like.
  • the substrate is preferably a resin film.
  • these resin films since they are excellent in transparency and have flexibility and versatility, they are at least one selected from the group consisting of polyesters, polycarbonates, polyimides, polyamides, cycloolefin polymers, and polyether sulfones. It is preferable that a polyester or a cycloolefin polymer is more preferable. More specifically, examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate. Examples of the polyamide include wholly aromatic polyamide, nylon 6, nylon 66, nylon copolymer, and the like.
  • cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof.
  • Examples thereof include apell (an ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals), arton (a norbornene polymer manufactured by JSR), zeonoa (a norbornene polymer manufactured by Nippon Zeon), and the like.
  • the film thickness of the substrate 12 illustrated in FIG. 1 may be determined according to the purpose of use, etc., but is within the range of 1 to 1000 ⁇ m from the viewpoint of flexibility and easy handling. The value is preferably in the range of 5 to 250 ⁇ m, more preferably in the range of 10 to 200 ⁇ m.
  • the base material may contain various additives such as an antioxidant, a flame retardant, and a lubricant as long as transparency and the like are not impaired.
  • a primer layer is a layer provided in order to improve the adhesiveness of a base material and a transparent conductive layer.
  • a urethane type resin an acrylic resin, a silane coupling agent, an epoxy resin, polyester, for example Known resins such as a resin and an ultraviolet curable resin can be used.
  • the gas barrier layer is preferably provided between the base material and the transparent conductive layer, and the material constituting the gas barrier layer is not particularly limited as long as it prevents the permeation of oxygen and water vapor. It is preferable that the gas barrier property is good. More specifically, examples of the constituent material include metals such as aluminum, magnesium, zirconium, titanium, zinc, and tin; silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, indium oxide, tin oxide, and oxide.
  • the gas barrier layer is more preferably composed of at least one selected from silicon oxide, silicon nitride, silicon oxynitride, and zinc tin oxide (ZTO).
  • the gas barrier layer may contain other compounding components such as various polymer resins, curing agents, anti-aging agents, light stabilizers, and flame retardants.
  • the method for forming the gas barrier layer is not particularly limited.
  • a method for forming the above-described material on a substrate by a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method, or the like A method in which a solution obtained by dissolving or dispersing the above material in an organic solvent is coated on a substrate by a known coating method, and the resulting coating film is appropriately dried to form a coating film. Examples thereof include a method of performing surface modification such as atmospheric pressure plasma, ion implantation, and lamp annealing.
  • the thickness of the gas barrier layer is not particularly limited, and is usually preferably a value in the range of 20 nm to 50 ⁇ m.
  • the film thickness of the gas barrier layer is more preferably set to a value within the range of 30 nm to 1 ⁇ m, and further preferably set to a value within the range of 40 nm to 500 nm.
  • a water vapor permeability as measured in an atmosphere of 90% RH is preferably not more than the value 0.1g / m 2 / day, 0.05g / m 2 / day or less of More preferably, the value is 0.01 g / m 2 / day or less.
  • the reason for this is that by setting such a value of water vapor transmission rate, the transparent conductive layer can be prevented from deteriorating and gas barrier properties excellent in moisture and heat resistance can be obtained.
  • it can measure by a well-known method as a water vapor transmission rate of a gas barrier layer, For example, it can measure using a commercially available water vapor transmission rate measuring apparatus.
  • the transparent conductive laminate 50 illustrated in FIG. 1A is formed by forming a transparent conductive layer 18 having a total thickness of 350 nm or less on one side or both sides on a substrate 12.
  • the transparent conductive layer 18 includes the first zinc oxide film 16 and the second zinc oxide film 10 along the film thickness direction from the substrate 12 side. Are formed in sequence, and the first zinc oxide film 16 and the second zinc oxide film 10 have the above-described configuration.
  • the wet heat characteristic of a transparent conductive laminated body can be adjusted suitably and precisely by combining the 2nd zinc oxide film
  • the light transmittance at a wavelength of 550 nm is preferably 70% or more and a value of 80% or more at a predetermined film thickness (350 nm or less). More preferably, the value is 90% or more.
  • the light transmittance at a wavelength of 550 nm is preferably 50% or more and more preferably 60% or more at a predetermined film thickness. More preferably, the value is 70% or more.
  • the initial specific resistance in the transparent conductive layer 18 of the transparent conductive laminate of the present invention is ⁇ 0, and the conditions are 500 hours at 60 ° C. and 95% relative humidity.
  • the ratio represented by ⁇ 500 / ⁇ 0 is preferably set to a value of 1.3 or less. More specifically, according to the present invention (first invention), the transparent conductive layer does not contain indium, the first zinc oxide film having a predetermined thickness containing gallium, and the predetermined film containing gallium and indium. Since the second zinc oxide film is used as the wet heat degradation suppressing layer, the initial specific resistance is maintained at a predetermined ratio by the synergistic effect of the two layers, and thus good. A transparent conductive laminate having excellent wet heat characteristics can be obtained. Note that the specific resistance ( ⁇ 500 , ⁇ 0 ) of the transparent conductive layer can be measured using a surface resistance measuring device as specifically described in Example 1.
  • Example 1 since the substrate has a transparent conductive layer in which a 100 nm In-GZO film and a 100 nm GZO film are sequentially formed, the In-GZO film has a remarkable wet heat deterioration suppressing effect. It is understood that the specific resistance ratio change is about 1.21 even after 500 hours. In Example 2, since the substrate has a transparent conductive layer in which a 100 nm GZO film and a 100 nm In-GZO film are sequentially formed, the In-GZO film is remarkable in Example 2. It is understood that the wet heat resistance effect is exhibited and the ratio change in specific resistance is about 1.03 even after 500 hours.
  • Example 3 since the substrate has a transparent conductive layer in which a 100 nm GZO film and a 20 nm In-GZO film are sequentially formed, the In-GZO film exhibits a remarkable wet heat resistance effect. In addition, it is understood that the ratio change of the specific resistance is about 1.1 even after 500 hours. Furthermore, since Example 4 has a transparent conductive layer in which a 100 nm GZO film and a 200 nm In-GZO film are sequentially formed on the base material, in Example 4, the In-GZO film has It is understood that a remarkable moist heat resistance effect is exhibited, and there is almost no change in the specific resistance ratio even after 500 hours.
  • the thickness of the transparent conductive film in the transparent conductive laminate (however, the thickness of the first transparent conductive film is constant at 100 nm) and the ratio before and after the environmental test.
  • the relationship with the resistance change will be described. That is, the horizontal axis of FIG. 6 shows the thickness of the second zinc oxide film, and the vertical axis shows the elapsed time when stored at 60 ° C. and a relative humidity of 95%. On the vertical axis, the ratio represented by ⁇ 500 / ⁇ 0 is taken. From the characteristic curve in FIG.
  • the surface resistivity (R) of the transparent conductive layer in the transparent conductive laminated body of this invention is a value of 1000 ohms / square or less. More specifically, when the surface resistivity exceeds 1000 ⁇ / ⁇ , conductivity suitable for the transparent conductive laminate may not be obtained. Therefore, the surface resistivity of the transparent conductive laminate is more preferably a value of 500 ⁇ / ⁇ or less, and further preferably a value of 200 ⁇ / ⁇ or less. In addition, about the measuring method of surface resistivity, it can measure using a surface resistance measuring apparatus so that it may demonstrate concretely in an Example.
  • the total thickness of the transparent conductive layer comprising the first zinc oxide film and the second zinc oxide film It is preferable to set (d) to a value within the range of 70 to 350 nm. This is because the wet heat characteristics of the transparent conductive layer can be remarkably improved even with a relatively thin film. More specifically, when the total thickness (d) of the transparent conductive layer is less than 70 nm, the wet heat characteristics of the transparent conductive layer may be significantly deteriorated. On the other hand, when the total thickness (d) of the transparent conductive layer exceeds 350 nm, the flexibility of the transparent conductive layer is remarkably lowered, and the usage application may be excessively limited.
  • the total thickness (d) of the transparent conductive layer composed of the first zinc oxide film and the second zinc oxide film is more preferably set to a value within the range of 80 to 350 nm (or 80 to 280 nm), More preferably, the value is in the range of 350 nm (or 100 to 250 nm).
  • the second embodiment is a transparent conductive laminate in which a transparent conductive layer having a total thickness of 350 nm or less is formed on at least one surface of a substrate, and the transparent conductive layer extends from the substrate side in the film thickness direction.
  • a second zinc oxide film and a first zinc oxide film are sequentially formed, and the first zinc oxide film is a zinc oxide film not containing indium and containing gallium as a dopant.
  • the second zinc oxide film contains indium and gallium as dopants, and has a film thickness of more than 50 nm.
  • the transparent conductive laminate 50 ′ illustrated in FIG. 1B is a transparent conductive laminate in which a transparent conductive layer is formed on one side or both sides of the substrate 12, In the transparent conductive layer, the second zinc oxide film 10 and the first zinc oxide film 16 are sequentially formed along the film thickness direction from the substrate side. Further, as shown in FIG. 1D, it is also a preferable aspect that a second zinc oxide film 10 ′ is further laminated on the first zinc oxide film 16. In this way, by combining the first zinc oxide film containing different gallium and indium and the second zinc oxide film containing gallium and indium with different compounding compositions and film thicknesses in combination, The wet heat characteristics of the transparent conductive laminate can be suitably and precisely adjusted.
  • the thickness of the second zinc oxide film exceeds 50 nm. This is because when the thickness of the second zinc oxide film is 50 nm or less, the specific resistance of the second zinc oxide film increases and the specific resistance of the transparent conductive layer may increase. On the other hand, if the film thickness of the second zinc oxide film becomes excessively thick, it takes a long time to form the second zinc oxide film, and productivity may be lowered or film warping may occur. Therefore, the thickness of the second zinc oxide film is more preferably set to a value within the range of 60 to 250 nm, and further preferably set to a value within the range of 70 to 150 nm. Note that the film thickness of the second zinc oxide film can be measured using a spectroscopic ellipsometer, as specifically described in Example 1.
  • the thickness (d1) of the first zinc oxide film is preferably set to a value of 250 nm or less. The reason for this is that if the thickness (d1) of the first zinc oxide film exceeds 250 nm, the formation of the first zinc oxide film takes an excessive amount of time, resulting in a decrease in productivity or transparency. This is because the total thickness (d) of the conductive layer is increased, the adhesion to the second zinc oxide film is lowered, and film warping may occur. However, when the film thickness (d1) of the first zinc oxide film is excessively thin, not only the specific resistance as the transparent conductive layer is increased, but also the wet heat characteristics may be significantly reduced.
  • the thickness (d1) of the first zinc oxide film is more preferably in the range of 20 to 230 nm, and still more preferably in the range of 30 to 150 nm.
  • the film thickness (d1) of the first zinc oxide film can also be measured using a spectroscopic ellipsometer, as specifically described in Example 1.
  • the first zinc oxide film and the second zinc oxide film are substantially the same as the contents of the first embodiment described above, except for the film thickness, and as the transparent conductive laminate. Since the characteristics are the same as described above, detailed description thereof will not be repeated.
  • 3rd Embodiment is related with 1st invention, Comprising: It is a manufacturing method of the transparent conductive laminated body formed by forming the transparent conductive layer whose total thickness (d) is 350 nm or less on the at least single side
  • Step of preparing a substrate, a first sintered body for zinc oxide film, and a second sintered body for zinc oxide film, respectively (2) On the substrate, using a sputtering method, Step (3) of forming a first zinc oxide film that does not contain indium as a dopant and contains gallium and has a film thickness exceeding 50 nm from the first sintered body for zinc oxide film
  • Step (1) is a step of preparing a base material and a sintered body. That is, the first zinc oxide film 16 illustrated in FIGS. 1A and 1C is formed from a sintered body containing zinc oxide as a main component and not containing indium oxide and containing gallium oxide. It is characterized by that.
  • the second zinc oxide film 10 is formed from a sintered body containing zinc oxide as a main component and containing at least gallium oxide and indium oxide. The details of the base material are the same as described above, and will be omitted.
  • the first zinc oxide film is formed from a sintered body containing zinc oxide as a main component and not containing indium oxide but containing gallium oxide. Will be described. That is, in the sintered body forming the first zinc oxide film, the blending amount of zinc oxide is 90 to 99.9% by weight (72.3 to 80% by weight as zinc) with respect to the total amount of the sintered body. ), And the blending amount of gallium oxide is preferably 0.1 to 10% by weight (0.07 to 7.4% by weight as gallium). The reason for this is that when the amount of gallium oxide is less than 0.1% by weight relative to the total amount of the sintered body, the amount of gallium contained in the first zinc oxide film after film formation is significantly reduced.
  • the blending amount of zinc oxide is 92 to 99% by weight (73.9 to 79.5% by weight as zinc) with respect to the total amount of the sintered body, and the blending amount of gallium oxide is 1.
  • a value in the range of ⁇ 8 wt% (0.74 to 6 wt% as gallium) is more preferable.
  • the blending amount of zinc oxide is set to a value within a range of 93 to 99% by weight (74.7 to 79.5% by weight as zinc) with respect to the total amount of the sintered body, and the blending amount of gallium oxide is 1 More preferably, the value is in the range of ⁇ 7% by weight (0.74 to 5.2% by weight as gallium).
  • the second zinc oxide film is formed from a sintered body containing zinc oxide as a main component and further containing indium oxide and gallium oxide.
  • the blending amount of zinc oxide is 15 to 99.98% by weight (12 to 80.3% by weight as zinc) with respect to the total amount of the sintered body.
  • a value within the range of 0.01 to 70% by weight (0.008 to 57.9% by weight as indium) is preferable.
  • the reason for this is that by using a ternary sintered body of zinc oxide-gallium oxide-indium oxide whose amount is controlled, a second zinc oxide film having excellent wet heat characteristics can be efficiently formed. This is because production efficiency can be improved. More specifically, when the blending amount of indium oxide is less than 0.01% by weight with respect to the total amount of the sintered body, the amount of indium contained in the second zinc oxide film after film formation is remarkably large. This is because there may be a case where sufficient wet heat characteristics are not obtained. On the other hand, when the amount of indium oxide exceeds 70% by weight, the amount of indium contained in the second zinc oxide film after film formation may increase remarkably.
  • the blending amount of zinc oxide is set to a value in the range of 23 to 99.4% by weight (as zinc, 18 to 79.9% by weight) with respect to the total amount of the sintered body, and the blending amount of gallium oxide is The value is in the range of 0.5 to 12% by weight (0.37 to 8.9% by weight as gallium), and the compounding amount of indium oxide is 0.1 to 65% by weight (0.083 as indium). More preferably, the value is within the range of ⁇ 53.8% by weight.
  • the blending amount of zinc oxide is set to a value within the range of 33 to 94.37% by weight (24.1 to 75.8% by weight as zinc) with respect to the total amount of the sintered body,
  • the amount is in the range of 5.4 to 10% by weight (4.1 to 7.4% by weight as gallium), and the compounding amount of indium oxide is 0.3 to 60% by weight (indium as 0% More preferably, the value is within the range of .25 to 49.6% by weight.
  • Step (2) is a method of forming the first zinc oxide film 16 on at least one surface of the substrate 12 as shown in FIG. .
  • a method for forming the first zinc oxide film a physical manufacturing method and a chemical manufacturing method represented by a chemical vapor deposition method can be given.
  • the sputtering method is preferable because a zinc oxide film can be easily formed. That is, since the composition of the first zinc oxide film to be formed can be easily controlled by forming by sputtering, the first zinc oxide film can be formed efficiently.
  • specific sputtering methods include DC sputtering method, DC magnetron sputtering method, RF sputtering method, RF magnetron sputtering method, DC + RF superposition sputtering method, DC + RF superposition magnetron sputtering method, counter target sputtering method, ECR sputtering method, dual magnetron.
  • the sputtering method etc. are mentioned.
  • the sputtering conditions are not particularly limited, but the back pressure is preferably 1 ⁇ 10 ⁇ 2 Pa or less, and more preferably 1 ⁇ 10 ⁇ 3 Pa or less.
  • the internal pressure is preferably set to a value in the range of 0.1 to 5 Pa, more preferably 0.2 to 1 Pa.
  • argon (Ar) or a mixed gas of argon (Ar) and oxygen (O 2 ) is used as a gas species to be introduced into the system by sputtering, but noble gases other than Ar, nitrogen (N 2 ) or the like may be used.
  • the mixing ratio (O 2 / (Ar + O 2 )) is preferably set to a value within the range of 0.01 to 20, and more preferably set to a value within the range of 0.1 to 10. preferable. This is because when the mixing ratio of argon and oxygen is in the above range, a conductive layer having a low specific resistance and a low reflectance can be formed.
  • the temperature of the substrate when forming the transparent conductive layer on the substrate is preferably set to a value within the range of 10 to 150 ° C. This is because, if the temperature of the substrate is a value within the range of 10 to 150 ° C., the transparent conductive layer can be suitably formed even with a substrate having a relatively low softening point.
  • Step (3) Step of Forming Second Zinc Oxide Film
  • the second zinc oxide film 10 is formed on the first zinc oxide film 16 as shown in FIG. It is a process.
  • the method for forming the second zinc oxide film is substantially the same as the method for forming the first zinc oxide film except for the target.
  • Step (4) Step of Forming First Zinc Oxide Film Step (4) is the same as the first zinc oxide film described above on the second zinc oxide film 10 as shown in FIG. This is a step of forming another first 'zinc oxide film 16' having the above composition. Since this process is the same as described above, the details are omitted.
  • [Fourth Embodiment] 4th Embodiment is related with 2nd invention, is a manufacturing method of the transparent conductive laminated body formed by forming the transparent conductive layer whose total thickness is 350 nm or less on the at least single side
  • the second zinc oxide film and the first zinc oxide film are sequentially formed along the film thickness direction from the substrate side, and include the following steps (1 ′) to (3 ′): Is a method for producing a transparent conductive laminate.
  • a sputtering method is performed on the substrate.
  • the fourth embodiment related to the second invention is a method for manufacturing the transparent conductive laminate illustrated in FIG. 1B and FIG.
  • This is a method for manufacturing transparent conductive laminates 50 ′ and 50 ′′ ′′ including the step of forming the second zinc oxide film 10 on the material 12 and then forming the first zinc oxide film 16.
  • step (4 ′) as shown in FIG. 1D, another 2 ′ zinc oxide having the same composition as that of the second zinc oxide film is formed on the first zinc oxide film 16.
  • a step of forming the film 10 ' may be included. Note that the details of each step are the same as those described in the first to third embodiments, and will be omitted.
  • the fifth embodiment relates to the first invention and the second invention, and is an electronic device characterized by using any of the transparent conductive laminates described above as a transparent electrode. More specifically, a liquid crystal display, an organic EL display, an inorganic EL display, an electronic paper, a solar cell, an organic transistor, an organic EL illumination, and an inorganic EL illumination each having a transparent electrode provided with a predetermined transparent conductive laminate. , Thermoelectric conversion devices, gas sensors and the like.
  • the electronic device of the present invention includes the transparent conductive laminate described in the first embodiment, it is excellent in wet heat characteristics and transparency, and can exhibit good electrical characteristics.
  • the present invention will be described in more detail by way of examples. However, the following description shows the present invention by way of example, and the present invention is not limited to these descriptions.
  • the first region and the second region having different compositions in the film thickness direction may be formed.
  • the thickness of the first region is usually less than 20 nm, the zinc oxide film is handled as a single layer for the sake of convenience even in the case of the following examples, even in the case of having such a plurality of regions.
  • alkali-free glass manufactured by Corning, Eagle XG, thickness: 700 ⁇ m
  • ZnO: Ga 2 O 3 94.3% by weight: 5.7% by weight
  • the following sputtering is performed on the alkali-free glass as a base material by the DC magnetron sputtering method using the above-described ternary sintered body.
  • a second zinc oxide film (In-GZO film, film thickness: 100 nm) was formed.
  • XPS measurement a first region of a thin film (less than 5 nm) is formed on the surface side of the zinc oxide film, that is, the surface opposite to the gas barrier layer, and a second region having a thickness of 95 nm is formed below the first region. It was confirmed separately that it was formed.
  • DC output 500W
  • Carrier gas Argon (Ar)
  • Deposition pressure 0.6Pa Deposition time: 35 sec.
  • the obtained second zinc oxide film is subjected to DC magnetron sputtering, using the above-described binary sintered body, A first zinc oxide film (GZO film, film thickness: 100 nm) was formed under the same sputtering conditions as described above.
  • the initial surface resistivity (R 0 ) in the transparent conductive layer of the obtained transparent conductive laminate was used as a surface resistance measuring device as a LOCESTA-GP MCP-T600 ( The measurement was performed using PROBE TYPE ASP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) as a probe and a probe at a temperature of 23 ° C. and 50% RH. Next, the obtained transparent conductive film was placed in an environment of 60 ° C. and 95% RH for 500 hours, taken out, then subjected to temperature control and humidity control in a 23 ° C. and 50% RH environment for 1 day. The surface resistivity (R 500 ) was measured.
  • Example 2 In Example 2, a first zinc oxide film (GZO film, film thickness: 100 nm) is formed on a substrate, and then a second zinc oxide film (In-GZO film, film thickness: 100 nm, predetermined thickness) A transparent conductive film was produced and evaluated in the same manner as in Example 1 except that the first region and the second region were formed. The obtained results are shown in Table 1.
  • Example 3 In Example 3, a transparent conductive laminate was produced and evaluated in the same manner as in Example 2 except that the thickness of the second zinc oxide film (In-GZO film) was 20 nm. The obtained results are shown in Table 1.
  • Example 4 a transparent conductive laminate was produced and evaluated in the same manner as in Example 2 except that the thickness of the second zinc oxide film (In-GZO film) was 200 nm. The obtained results are shown in Table 1.
  • Comparative Example 1 In Comparative Example 1, the second zinc oxide film (In-GZO film) was not formed, but only the first zinc oxide film (GZO film, film thickness 200 nm) was formed. Conductive laminates were manufactured and evaluated. The obtained results are shown in Table 1.
  • Comparative Example 2 In Comparative Example 2, the second zinc oxide film (In-GZO film) was not formed, but only the first zinc oxide film (GZO film, film thickness 100 nm) was formed. Conductive laminates were manufactured and evaluated. The obtained results are shown in Table 1.
  • the transparent conductive laminate of the present invention is a transparent conductive laminate in which a transparent conductive layer is formed on at least one surface on a substrate, and the transparent conductive layer is By having the first zinc oxide film and the second zinc oxide film having a predetermined configuration, a transparent conductive laminate having good electrical characteristics and excellent wet heat characteristics can be efficiently obtained. . Therefore, the transparent conductive laminate of the present invention can be used in electrical products, electronic components, image display devices (organic electroluminescent elements, inorganic electroluminescent elements, liquid crystal display devices, electronic paper, etc.), thermoelectrics that require predetermined wet heat characteristics. It is expected to be used effectively as a transparent electrode in various applications such as conversion devices and solar cells.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Non-Insulated Conductors (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

La présente invention concerne un stratifié conducteur transparent présentant d'excellentes caractéristiques à la chaleur humide, un procédé de fabrication dudit stratifié conducteur transparent, et un dispositif électronique formé à l'aide d'un tel stratifié conducteur transparent. En d'autres termes, la présente invention concerne un stratifié conducteur transparent qui est formé par formation d'une couche conductrice transparente ayant une épaisseur totale de 350 nm ou moins sur au moins un côté d'un substrat, et est: soit un stratifié conducteur transparent (première invention) qui comporte une couche conductrice transparente qui est formée par formation séquentielle, à partir du côté substrat dans la direction de l'épaisseur de la couche, d'un premier film d'oxyde de zinc et d'un second film d'oxyde de zinc, ledit premier film d'oxyde de zinc étant un film d'oxyde de zinc qui ne contient pas d'indium, contient du gallium et a une épaisseur de film supérieure à 50 nm, et ledit second film d'oxyde de zinc étant un film d'oxyde de zinc qui contient de l'indium et du gallium comme dopants; soit un stratifié conducteur transparent (seconde invention) qui est formé par formation du premier film d'oxyde de zinc et du second film d'oxyde dans l'ordre inverse, l'épaisseur de film du second film d'oxyde de zinc étant supérieure à 50 nm.
PCT/JP2015/053364 2014-02-07 2015-02-06 Stratifié conducteur transparent, procédé de fabrication de stratifié conducteur transparent, et dispositif électronique formé à l'aide du stratifié conducteur transparent WO2015119240A1 (fr)

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TWI635962B (zh) 2018-09-21

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