CN111868293A - Transparent oxide laminated film, method for producing transparent oxide laminated film, and transparent resin substrate - Google Patents

Transparent oxide laminated film, method for producing transparent oxide laminated film, and transparent resin substrate Download PDF

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Publication number
CN111868293A
CN111868293A CN201980019836.7A CN201980019836A CN111868293A CN 111868293 A CN111868293 A CN 111868293A CN 201980019836 A CN201980019836 A CN 201980019836A CN 111868293 A CN111868293 A CN 111868293A
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film
transparent oxide
transparent
laminated film
oxide
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桑原正和
仁藤茂生
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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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
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/09—Layered products comprising a layer of metal comprising metal 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 comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • C04B35/457—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates based on tin oxides or stannates
    • 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
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3464—Sputtering using more than one target
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention provides a transparent oxide laminated film with excellent transparency, good water vapor barrier performance and chemical reagent resistance, a manufacturing method thereof and a transparent resin substrate using the transparent oxide laminated film. A transparent oxide laminated film is formed by laminating a plurality of transparent oxide films containing Zn and Sn, and the transparent oxide laminated film is composed of amorphous transparent oxide films with different metal atom ratios of Zn and Sn in each layer. Also disclosed is a method for producing a transparent oxide laminated film, wherein a target composed of a Sn-Zn-O oxide sintered body is used for sputtering, and at least a 1 st target and a 2 nd target are used for forming the transparent oxide laminated film, wherein the 1 st target comprises an oxide sintered body having a metal atom ratio of Sn/(Zn + Sn) of 0.18 to 0.29 inclusive, and the 2 nd target comprises an oxide sintered body having a metal atom ratio of Sn/(Zn + Sn) of 0.44 to 0.90 inclusive.

Description

Transparent oxide laminated film, method for producing transparent oxide laminated film, and transparent resin substrate
Technical Field
The present invention relates to a transparent oxide laminated film, a method for producing a transparent oxide laminated film, and a transparent resin substrate. More particularly, the present invention relates to an amorphous transparent oxide laminate film having excellent water vapor barrier properties and chemical resistance, a method for producing the same, and a transparent resin substrate on which the transparent oxide laminate film is formed. This application claims priority based on japanese patent application No. 2018-.
Background
A water vapor barrier resin substrate obtained by covering the surface of a transparent resin substrate such as a plastic substrate or a film substrate with a metal oxide film such as silicon oxide or aluminum oxide is used for packaging purposes for preventing the intrusion of water vapor and preventing the degradation of foods, medicines, and the like. In recent years, the present invention is also used for liquid crystal display elements, solar cells, electroluminescence display elements (EL elements), Quantum Dot (QD) display elements, quantum dot films (QD films), and the like.
In recent years, as the display devices have been increasingly developed, there have been demands for a water vapor barrier transparent resin substrate used for electronic devices, particularly display devices, such as a light weight and a large size, and also demands for flexibility in shape freedom, curved surface display, and the like. Therefore, the glass substrate used so far is strictly handled, and therefore, a transparent resin substrate is beginning to be used.
However, since the transparent resin substrate has a lower water vapor barrier property than a glass substrate, water vapor permeates through the substrate, and there is a problem that the EL display element, the QD display element, and the like are deteriorated. In addition, there are problems in molding the base material as follows: the water vapor barrier layer is damaged by etching or the like caused by a chemical solution or the like used for patterning the adhesive layer or the transparent conductive layer, and the barrier function is impaired, so that water vapor passes through the substrate, and the EL display element, the QD display element, or the like is deteriorated. In order to solve such a problem, development of a transparent resin substrate in which a metal oxide film is formed on a resin base material has been carried out.
For example, patent document 1 describes a water vapor barrier transparent resin substrate in which a transparent conductive film of tin oxide or the like is formed on a transparent film by a sputtering method. According to the description of patent document 1, it is described that the water vapor transmission rate obtained by the Mocon method is less than 0.01g/m2/day。
Patent document 2 proposes a barrier film obtained by laminating an inorganic film and an organic film. Patent document 2 describes that the water vapor transmission rate at this time is 0.01g/m2The inorganic film has a thickness of 30nm to 1 μm and the organic layer has a thickness of 10nm to 2 μm, respectively, below day.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2005-103768
Patent document 2: japanese patent No. 5161470
Disclosure of Invention
Problems to be solved by the invention
In recent years, with the practical use of EL display elements and QD display elements, in the case of displays such as organic EL displays, the following problems are known: when water vapor is mixed into the organic EL display element, damage due to moisture greatly affects the interface between the cathode layer and the organic layer, and peeling between the organic layer and the cathode portion and black spots as non-light-emitting portions occur, resulting in significant performance degradation. The Water Vapor Transmission Rate (WVTR) required for the water vapor barrier transparent resin substrate usable for these displays is said to be 0.01g/m 2A value of 0.005g/m or less per day2And/day is less.
In addition, these displays are also required to be flexible, and the demand for thinning of the water vapor barrier transparent resin substrate is also increasing in many cases. The thickness of the barrier film is required to be 100nm or less. Further, chemical resistance is also strongly demanded. Regarding chemical resistance, in order to protect the metal oxide layer from chemical agents such as acids, bases, and organic solvents, studies have also been made to provide a chemical resistance layer made of an organic compound on the metal oxide layer.
For example, the chemical resistance is to an alkaline aqueous solution or an acidic aqueous solution used in an etching step when patterning a transparent electrode of a barrier film with a transparent electrode. In general, the etching step of the transparent electrode is a step of coating a resist, exposing the resist, developing the resist, etching the transparent electrode, and stripping the resist, and an alkaline aqueous solution is used in the resist developing step and the resist stripping step, and an acidic aqueous solution is used in the etching step of the transparent electrode. In addition, when forming the base material, an acidic or alkaline solvent may be contained in the adhesive material or the sealant of the adhesive layer. Accordingly, when the water vapor barrier transparent layer is partially etched, the water vapor barrier property is deteriorated, and thus chemical resistance is regarded as important. Since elements such as liquid crystal elements, organic EL elements, TFT elements, semiconductor elements, and solar cells are formed to have low resistance to water and oxygen, if the water vapor barrier transparent layer is etched by these chemical solutions, the following problems occur: when the display is displayed, black spots and defective dots are generated, and the semiconductor element and the solar cell do not function. In order to solve this problem, development of a transparent resin substrate in which a metal oxide film is formed on a resin base material has been demanded.
On the other hand, in patent document 1, the water vapor transmission rate is measured by the Mocon method, but in the measurement by the Mocon method, it is difficult to accurately measure 0.01g/m2Below/day, there is still a question about the water vapor barrier properties of the actual film. In addition, since the film used was 200 μm, the thickness of the barrier filmThe thickness is 100 to 200nm, so the flexibility is poor.
Patent document 2 proposes a barrier film obtained by laminating an inorganic film and an organic film, but since film formation processes are different between the inorganic film and the organic film, it is necessary to perform film lamination by different processes, and it is considered that productivity is deteriorated and characteristics are deteriorated due to foreign matter or the like. In addition, it describes: in order to achieve a water vapor transmission rate of 0.01g/m2The flexibility is poor because the structure must be 3 or more layers and the organic layer must be about 500nm or less per day.
Therefore, when a film formed by a sputtering method is used as a barrier film used for an EL display element, a QD display element, or the like, a thin film thickness and a good water vapor transmission barrier property are further required, and high chemical resistance is also required.
The present invention has been made in view of these demands, and an object thereof is to provide a transparent oxide laminated film having excellent transparency, good water vapor barrier performance, and chemical resistance, a method for producing the same, and a transparent resin substrate using the transparent oxide laminated film.
Means for solving the problems
In view of the above problems, the present inventors have intensively analyzed compositions suitable for water vapor barrier performance and chemical resistance in a laminated film composed of a plurality of amorphous transparent oxide films having different metal atom ratios of Zn to Sn, and as a result, have completed the present invention.
That is, one embodiment of the present invention is a transparent oxide laminated film in which a plurality of transparent oxide films containing Zn and Sn are laminated, the transparent oxide laminated film being composed of amorphous transparent oxide films having different metal atom ratios of Zn to Sn in each layer.
According to one aspect of the present invention, a transparent oxide laminated film having excellent water vapor barrier performance and chemical resistance can be produced by forming a layer having water vapor barrier performance and a layer having chemical resistance by changing the metal atom ratio of Zn to Sn in each layer.
In this case, in one embodiment of the present invention, at least the 1 st transparent oxide film having Sn/(Zn + Sn) of 0.18 to 0.29 in terms of the metal atom number ratio and the 2 nd transparent oxide film having Sn/(Zn + Sn) of 0.44 to 0.90 in terms of the metal atom number ratio may be included.
When Sn/(Zn + Sn) is 0.18 to 0.29, the water vapor barrier performance is excellent, and when Sn/(Zn + Sn) is 0.44 to 0.90, the transparent oxide film having excellent chemical resistance is obtained.
In one embodiment of the present invention, the transparent oxide film of at least one of the layers may contain Ta and Ge, and in the atomic ratio of Zn, Sn, Ta and Ge, Ta/(Zn + Sn + Ge + Ta) is 0.01 or less and Ge/(Zn + Sn + Ge + Ta) is 0.04 or less.
Ta and Ge are components derived from the target, and therefore, the conductivity of the target itself can be improved, and the film formation rate can be increased, and the film formation can be stabilized by increasing the target density.
In one embodiment of the present invention, the thickness of the transparent oxide laminated film may be 100nm or less.
By setting the film thickness to 100nm or less, a transparent oxide laminated film having excellent flexibility can be obtained.
In one embodiment of the present invention, the transparent oxide laminated film may have a water vapor transmission rate of 0.001g/m, which is obtained by a prescribed pressure difference method in accordance with JIS K71292And/day is less.
By satisfying the above requirements, it can be said that the transparent oxide laminated film has excellent water vapor barrier properties.
In one embodiment of the present invention, the transparent oxide laminated film may have chemical resistance to acid or alkali, and the change in color difference Δ Eab between before and after immersion in 5% hydrochloric acid or 5% sodium hydroxide solution for 5 minutes may be 1.0 or less.
By satisfying the above requirements, it can be said that the transparent oxide laminated film has excellent chemical resistance.
In one embodiment of the present invention, the transparent oxide laminated film may have chemical resistance to an acid or an alkali, and the amount of change in film between 5% hydrochloric acid or 5% sodium hydroxide solution after immersion for 5 minutes may be 2.0nm or less.
By satisfying the above requirements, it can be said that the transparent oxide laminated film has excellent chemical resistance.
Another embodiment of the present invention is a method for producing a transparent oxide laminated film by sputtering using a target made of an Sn — Zn — O-based oxide sintered body, wherein the transparent oxide laminated film is formed using at least a 1 st target having an oxide sintered body in which Sn/(Zn + Sn) is 0.18 to 0.29 in terms of a metal atom ratio and a 2 nd target having an oxide sintered body in which Sn/(Zn + Sn) is 0.44 to 0.90 in terms of a metal atom ratio.
According to another aspect of the present invention, a transparent oxide film having excellent water vapor barrier performance can be formed by sputtering using the 1 st target, and a transparent oxide film having excellent chemical resistance can be formed by sputtering using the 2 nd target.
Another embodiment of the present invention is a transparent resin substrate obtained by forming the transparent oxide laminated film on at least one surface of a transparent resin substrate.
According to another aspect of the present invention, by forming the transparent oxide laminated film, a transparent resin substrate having both excellent water vapor barrier properties and chemical resistance can be produced.
In this case, in another embodiment of the present invention, the transparent oxide film having Sn/(Zn + Sn) of 0.44 to 0.90 in terms of the metal atom number ratio may be the outermost layer.
Such a transparent oxide film is preferably formed on the outermost layer of the transparent resin substrate because it has chemical resistance.
Effects of the invention
According to the present invention, a transparent oxide laminated film having excellent transparency, good water vapor barrier performance, and chemical resistance can be provided by dc sputtering with high mass productivity.
Detailed Description
The transparent oxide laminated film, the method for producing the transparent oxide laminated film, and the transparent resin substrate according to the present invention will be described in the following order. The present invention is not limited to the following examples, and can be modified as desired without departing from the scope of the present invention.
1. Transparent oxide laminated film
2. Method for producing transparent oxide laminated film
3. Transparent resin substrate
< 1. transparent oxide laminated film >
One embodiment of the present invention is a transparent oxide laminated film formed by laminating a plurality of transparent oxide films containing Zn and Sn, the transparent oxide laminated film being composed of amorphous transparent oxide films having different metal atom ratios of Zn to Sn in each layer. By changing the metal atomic ratio of Zn to Sn in each layer in this manner, a layer having water vapor barrier performance and a layer having chemical resistance are formed, respectively, whereby a transparent oxide laminated film having excellent water vapor barrier performance and chemical resistance can be produced.
The amorphous transparent oxide laminated film of the present invention (hereinafter, also simply referred to as an oxide laminated film) is mainly used as a water vapor barrier film. A surface of a plastic substrate, a film substrate, or a flexible display element such as a liquid crystal display element, a solar cell, or an Electroluminescence (EL) display element is covered with a metal oxide film by a sputtering method, and is used for the purpose of preventing deterioration by blocking water vapor or the like.
This is because: when the oxide laminated film is a crystalline film, grain boundaries exist in the film, and water vapor passes through the grain boundaries, and therefore, the water vapor barrier performance is lowered. In addition, in patent document 1, a tin oxide-based film is proposed as the amorphous film, but when a tin oxide-based film is formed by a sputtering method, a target material constituting a sputtering target used for sputtering may use a tin oxide-based film having the same composition as the film. The tin oxide-based target generally has high acid resistance but has a low relative density, and thus there are many problems such as the target breaking during sputtering and the like, which makes it impossible to stably form a film. The transparent oxide laminated film according to the present invention eliminates the above-mentioned concerns by using a Sn — Zn — O sputtering target described later.
That is, an oxide sputtering laminated film according to an embodiment of the present invention is an amorphous transparent oxide film containing Zn and Sn, and is characterized by being formed by laminating transparent oxide films having different metal atom ratios of Zn and Sn. The number of transparent oxide films to be stacked is not particularly limited as long as it is at least 2 layers. The 2 transparent oxide films having different metal atom ratios of Zn and Sn are preferably the 1 st transparent oxide film having a Sn/(Zn + Sn) ratio of 0.18 to 0.29 in terms of metal atom ratio, and the 2 nd transparent oxide film having a Sn/(Zn + Sn) ratio of 0.44 to 0.90 in terms of metal atom ratio.
In the 1 st transparent oxide film, by setting Sn/(Zn + Sn) to 0.18 or more and 0.29 or less in terms of the metal atom number ratio, a good water vapor barrier performance (low water vapor transmission rate) can be obtained.
When the metal atom number ratio Sn/(Zn + Sn) is less than 0.18, SnO is caused2The ratio is decreased, so that the deposition of ZnO having high crystallinity increases, the number of portions (microcrystalline state) in which partial crystallization occurs in the film increases, the inflow of water vapor from the grain boundary increases, and an oxide sputtered film having a desired water vapor barrier property cannot be obtained.
On the other hand, when the metal atom number ratio Sn/(Zn + Sn) is more than 0.29, SnO is caused 2The rate increases, so that the stress of the film increases, and further, heat generation during film formation increases, and peeling of the film and damage to the substrate occur, and an oxide sputtered film having a water vapor barrier property that can be used for OLEDs, QDs, and the like cannot be obtained.
In addition, the 2 nd transparent oxide film can obtain good chemical resistance by setting Sn/(Zn + Sn) to 0.44 or more and 0.90 or less in terms of the metal atom number ratio.
Zinc oxide (ZnO) is easily dissolved in chemical reagents such as acids and alkalis, and has a disadvantage of lacking resistance to chemical reagents such as acids and alkalis. It is difficult to perform high-definition patterning processing by wet etching, for example. But tin oxide (SnO)2) Has the characteristic of extremely high resistance to chemical agents. Therefore, the second transparent oxygen containing Zn and Sn is used as the second transparent oxygenSnO is a main component of the film2Thereby obtaining chemical resistance such as acid and alkali resistance.
When the metal atom ratio Sn/(Zn + Sn) is less than 0.44, the ZnO ratio increases, and the chemical resistance is poor.
On the other hand, when the metal atomic number ratio Sn/(Zn + Sn) is more than 0.90, the density of the sintered compact of the target used in sputtering is low, and the possibility of occurrence of a failure in cracking of the sintered compact during sputtering is high.
The 1 st transparent oxide film and the 2 nd transparent oxide film are made of the same kind of oxide. Therefore, a sputtering method which is widely used in industry can be used for film formation. The sputtering method is effective in that the film can be formed with high mass productivity and with a uniform film thickness. Further, although it depends on the sputtering apparatus, in the case of a sputtering apparatus provided with a plurality of targets, targets for the 1 st oxide film and the 2 nd oxide film (the 1 st target and the 2 nd target described later) can be provided and sputtering can be performed simultaneously, and productivity is excellent. Since both the 1 st oxide film and the 2 nd oxide film are amorphous oxide films containing Zn and Sn, the adhesion of the films at the time of lamination is high, and since the films are amorphous, the film stress generated at the time of film formation can be relaxed.
Preferably, at least one of the 1 st transparent oxide film and the 2 nd transparent oxide film further contains Ta and Ge, and Ta/(Zn + Sn + Ge + Ta) in the metal atomic ratio of Ta to Zn, Sn and Ge is 0.01 or less, and Ge/(Zn + Sn + Ge + Ta) in the metal atomic ratio of Ge to Zn, Sn and Ta is 0.04 or less.
Even when Ta or Ge is contained, an amorphous film structure can be easily obtained because the crystallization temperature is 600 ℃ or higher. Further, since the crystallization temperature is high, the amorphous state can be easily maintained even when there is a thermal influence in the mass production process. In addition, by adding Ta and Ge in the above ratio, the characteristics of the sputtering target containing Zn and Sn can be further improved.
Hereinafter, the additive elements (Ta, Ge) will be briefly described. The sputtering target is obtained by bonding (joining) an oxide sintered body composed of Sn — Zn alone to a backing plate composed of a copper material, a stainless steel material, or the like, using a joining material such as indium (In), or the like.
In the oxide sintered body composed of only Sn — Zn composition, the conductivity is insufficient and the resistivity value is large in some cases. In sputtering, as the resistivity value increases, sputtering with a larger energy is required, and the film deposition rate cannot be increased. Therefore, it is necessary to increase the conductivity of the sintered body for a target. Zn in oxide sintered body2SnO4、ZnO、SnO2Is a substance having poor conductivity, and therefore, even if the mixing ratio is adjusted, the compound phase, ZnO or SnO is adjusted2The amount of (3) also does not significantly improve the conductivity.
Therefore, Ta (tantalum) is preferably added. Ta will react with Zn and Zn in ZnO phase2SnO4Zn or Sn, SnO in phase2Sn in the phase is substituted and dissolved in a solid solution, so that a ZnO phase having a wurtzite-type crystal structure and Zn having a spinel-type crystal structure are not formed2SnO4Phase, and SnO of rutile type crystal structure2Compound phases other than the phase. By adding Ta, the conductivity can be improved while maintaining the density of the oxide sintered body.
Further, the sintered density of the oxide sintered body composed of Sn — Zn alone is about 90%, and may not be said to be sufficient. If the density of the oxide sintered body is low, there is a problem that stable film formation cannot be performed due to cracking of the oxide sintered body during sputtering.
Therefore, a predetermined amount of Ge (germanium) is preferably added. In the oxide sintered body, Ge reacts with Zn and Zn in the ZnO phase2SnO4Zn or Sn, SnO in phase2Sn in the phase is substituted and dissolved in a solid solution, so that a ZnO phase having a wurtzite-type crystal structure and Zn having a spinel-type crystal structure are not formed2SnO4Phase, and SnO of rutile type crystal structure2Compound phases other than the phase. Addition of Ge serves to densify the oxide sintered body. This makes it possible to set the sintered density of the oxide sintered body to a higher density.
Therefore, it is preferable that the oxide sintered body further contains Ta and Ge, and Ta/(Zn + Sn + Ge + Ta) of the metal atomic ratio of Ta to Zn, Sn, and Ge is 0.01 or less, and Ge/(Zn + Sn + Ge + Ta) of the metal atomic ratio of Ge to Zn, Sn, and Ta is 0.04 or less. The approximate lower limit of the effect obtained by adding Ta and Ge is 0.0005 in the metal atom ratio together with Ta and Ge.
When Ta/(Zn + Sn + Ge + Ta) is more than 0.01 in the metal atom number ratio of Ta to Zn, Sn, Ge, another compound phase is formed, for example, Ta2O5、ZnTa2O6And a compound phase, and therefore, the conductivity cannot be greatly improved. When Ge/(Zn + Sn + Ge + Ta) is greater than 0.04 in the metal atom number ratio of Ge to Zn, Sn and Ta, another compound phase, for example, Zn, is formed 2Ge3O8And the density of the oxide sintered body is lowered due to the compound phase, and the target is easily broken during sputtering.
Even if sputtering is performed using a target to which Ta and Ge are added, the oxide sputtering film formed will not be affected. For example, no effect on the water vapor transmission rate was observed. The same applies to chemical resistance. Therefore, even if Ta is contained in a ratio of Ta/(Zn + Sn + Ge + Ta) of 0.01 or less and Ge/(Zn + Sn + Ge + Ta) of 0.04 or less, an amorphous oxide sputtered film maintaining good characteristics can be obtained without deteriorating the water vapor barrier performance. The same applies to chemical resistance.
The thickness of the oxide laminated film is preferably 100nm or less, and more preferably 90nm or less. By setting the film thickness as described above, an oxide laminated film having excellent flexibility can be provided.
The thickness of the transparent oxide laminated film obtained by combining the 1 st oxide film and the 2 nd oxide film may be 100nm or less, preferably 90nm or less. Therefore, the thickness of each of the 1 st oxide film and the 2 nd oxide film is not limited.
In one embodiment of the present invention, the oxide laminated film preferably has a water vapor transmission rate of 0.001g/m according to JIS K7129 and a predetermined pressure difference method 2And/day is less. As described above, the Water Vapor Transmission Rate (WVTR) required for a water vapor barrier transparent resin substrate usable for a display is said to be 0.01g/m2Less than or equal to/day, preferably0.005g/m2And/day is less. The oxide laminated film of the present invention has a water vapor transmission rate of 0.001g/m2The ratio,/day or less, is sufficiently applicable to this.
The water vapor transmission rate is mainly affected by the 1 st oxide film, and particularly by the film thickness. Regarding the water vapor transmission rate, the thicker the film thickness, the smaller the water vapor transmission rate. Therefore, the film thickness is appropriately set in consideration of the required water vapor transmission rate.
In one embodiment of the present invention, the 2 nd oxide film has chemical resistance. The evaluation of the chemical resistance was evaluated by the color difference Δ Eab. The color difference was evaluated using the L.a.b.0 color system (CIE 1976). L1 a 2b 3, L4 is lightness, a 5, b 6 are hue and chroma, and L7 is a value of 0 to 100, and the larger the value is, the more white the color becomes. a 8 is an axis from red to green, + a is a red direction, -a is a green direction, b is an axis from yellow to blue, + b is a yellow direction, -b is a blue direction, and when a and b are all 0, the color is achromatic. The color difference Δ Eab is calculated by the color difference calculation formula of CIE 1976. Before and after the evaluation, L, a, b are measured, and the difference between the two is expressed as DeltaL, Deltaa, Deltab, and the color difference DeltaEab is expressed by 2+(Δa＊)2+(Δb＊)2)1/2And (4) obtaining.
In one embodiment of the present invention, chemical resistance is confirmed by chemical resistance to acids and bases. The acid resistance was evaluated by immersing the steel sheet in 5% hydrochloric acid for 5 minutes, and the alkali resistance was evaluated by immersing the steel sheet in 5% sodium hydroxide solution for 5 minutes, and then evaluating the change in the color difference Δ Eab. Presume that: when the color difference Δ Eab is large, the color tone changes before and after the treatment, and the oxide laminated film is eluted by the chemical agent and discolored. If the change value of the color difference Δ Eab is 1.0 or less, more preferably 0.5 or less, the oxide laminated film is judged to have less elution by the chemical agent and chemical resistance.
In one embodiment of the present invention, the chemical resistance can be confirmed by a change in film thickness after acid or alkali immersion. The thickness change before and after immersion in the chemical agent can be verified as follows: the amounts of Zn and Sn dissolved in the chemical reagent with which the sample was immersed were confirmed by the ICP-AES method, and the amount of decrease in film thickness (amount of change in film) was checked from the results, film formation area, and film density. Chemical resistance can be determined if the amount of decrease in film thickness (amount of change in film) after immersion in 5% hydrochloric acid for 5 minutes is 2.0nm or less with respect to acid resistance and the amount of decrease in film thickness (amount of change in film) after immersion in 5% sodium hydroxide solution for 5 minutes is 2.0nm or less with respect to alkali resistance.
As described above, tin oxide (SnO)2) Has the characteristic of extremely high resistance to chemical agents. The main component of the amorphous 2 nd transparent oxide film containing Zn and Sn is SnO2And Sn/(Zn + Sn) is set to 0.44-0.90 in terms of metal atomic number ratio, so that the color difference Delta Eab change value can be set to 0.5 or less, and the film change amount can be set to 2.0nm or less.
As described above, the transparent oxide laminated film according to one embodiment of the present invention can have excellent transparency, good water vapor barrier properties, and chemical resistance.
< 2. method for producing transparent oxide laminated film
Next, a method for producing a transparent oxide laminated film according to an embodiment of the present invention will be described. One embodiment of the present invention is a method for producing a transparent oxide laminated film by sputtering using a target composed of an Sn — Zn — O-based oxide sintered body, wherein the transparent oxide laminated film is formed using at least a 1 st target having an oxide sintered body in which Sn/(Zn + Sn) is 0.18 to 0.29 in terms of a metal atom ratio and a 2 nd target having an oxide sintered body in which Sn/(Zn + Sn) is 0.44 to 0.90 in terms of a metal atom ratio.
As described above, in the method for producing a transparent oxide laminated film according to one embodiment of the present invention, sputtering is performed using a Sn — Zn — O oxide sintered body to obtain 2 amorphous laminated films having different metal atomic ratios of Zn and Sn. That is, by sputtering using the 1 st target, a transparent oxide film having excellent water vapor barrier performance can be formed, and by sputtering using the 2 nd target, a transparent oxide film having excellent chemical resistance can be formed.
A target is prepared which is composed of a 1 st target used for sputtering a 1 st oxide film and a 2 nd target used for sputtering a 2 nd oxide film, wherein the 1 st target is a sintered body in which Sn/(Zn + Sn) which is the metal atomic ratio of Zn to Sn contained in the oxide sintered body is 0.18 to 0.29, and the 2 nd target is a sintered body in which Sn/(Zn + Sn) which is the metal atomic ratio of Zn to Sn contained in the oxide sintered body is 0.44 to 0.90. The technical meaning of the composition range of each sintered body is as described above.
The total film thickness of the sputtered oxide laminated film is preferably 100nm or less, and more preferably 90nm or less. As described above, by doing so, an oxide laminated film having good water vapor barrier properties and further excellent flexibility can be provided. The thickness of each of the 1 st oxide film and the 2 nd oxide film is not particularly limited.
The sputtering may be performed using a sputtering target composed of the oxide sintered body. The sputtering apparatus is not particularly limited, and a dc magnetron sputtering apparatus or the like can be used.
As a sputtering condition, the degree of vacuum in the chamber was adjusted to 1X 10-4Pa or less. An inert gas is introduced into the atmosphere in the chamber. The inert gas is argon gas or the like, and the purity is preferably 99.999 mass% or more. The inert gas contains 4 to 10% by volume of oxygen with respect to the total gas flow rate. The oxygen concentration has an influence on the surface resistance value of the film, and therefore, the oxygen concentration is set so as to have a predetermined resistance value. Then, a predetermined dc power supply is applied between the sputtering target and the base material, and plasma is generated by a dc pulse to perform sputtering, thereby forming a film. The film thickness is controlled by the film formation time.
The sputtering is to form the 2 nd oxide film after forming the 1 st oxide film. In this case, when a plurality of targets can be provided in the sputtering apparatus, the 1 st target for the 1 st oxide film and the 2 nd target for the 2 nd oxide film can be provided and sputtering can be performed continuously. Further, the target is of the same kind, and the film has good adhesion and affinity.
As described above, according to the method for producing a transparent oxide laminated film according to one embodiment of the present invention, an oxide laminated film having excellent transparency, good water vapor barrier performance, and chemical resistance can be obtained by dc sputtering with high mass productivity.
< 3. transparent resin substrate
The transparent resin substrate according to one embodiment of the present invention is obtained by forming at least 2 amorphous transparent oxide laminated films having different metal atom ratios of Zn to Sn on a transparent base material. Preferably, the transparent oxide laminated film is formed on at least one surface of the substrate, and Sn/(Zn + Sn) at a metal atom ratio of Zn to Sn in the 1 st oxide film is 0.18 to 0.29 inclusive, and Sn/(Zn + Sn) at a metal atom ratio of Zn to Sn in the 2 nd oxide film is 0.44 to 0.90 inclusive. The thickness of the transparent oxide laminated film is preferably 100nm or less, and more preferably 90nm or less.
As the transparent substrate, polyethylene terephthalate, polyethylene, naphthalate, polycarbonate, polysulfone, polyethersulfone, polyarylate, cycloolefin polymer, fluororesin, polypropylene, polyimide resin, epoxy resin, or the like can be used. The thickness of the transparent resin substrate is not particularly limited, but is preferably 50 to 150 μm in consideration of flexibility, cost, and device requirements.
The sputtering method on the transparent substrate may be performed as described in the method for producing a transparent oxide laminated film. The technical meanings of the above-mentioned appropriate metal atom ratio of Zn to Sn, film thickness, and the like are as described above.
The transparent resin substrate according to one embodiment of the present invention is obtained by forming an amorphous and transparent oxide sputtering film containing Zn and Sn and having a water vapor barrier property on at least one surface of a base material, and may be laminated with another film interposed therebetween. For example, a silicon oxide film, a silicon oxynitride film, a resin film, a wet coating film, a metal film, an oxide film, or the like may be formed on the substrate, and then the oxide sputtered film may be formed as a water vapor barrier layer on at least one of the substrates.
In one embodiment of the present invention, the 2 nd oxide film is preferably an outermost layer. That is, the 2 nd oxide film having chemical resistance is preferably formed on the outer side (surface side) of the 1 st oxide film. Specifically, in the subsequent step, the 2 nd oxide film is formed on the outermost surface of the surface side using an acid or an alkaline chemical agent in the step of forming the transparent electrode, the step of applying an adhesive, or the like. The 1 st oxide film mainly has a water vapor barrier property, and when this surface is formed on the front surface side, the chemical resistance is weak, and there is a high possibility that the water vapor barrier property is also impaired by the chemical agent. By forming the 2 nd oxide film of the present invention on the outer side (surface side) of the 1 st oxide film, both the chemical resistance and the water vapor barrier property can be maintained.
For example, a flexible OLED display element, a flexible QD display element, and a QD film, which are one of flexible display elements, can be formed using the transparent resin substrate according to one embodiment of the present invention.
As described above, the transparent resin substrate according to one embodiment of the present invention has excellent transparency, good water vapor barrier performance, and chemical resistance by dc sputtering with high mass productivity.
Examples
Hereinafter, examples of the present invention will be described specifically by referring to comparative examples, but the technical scope of the present invention is not limited to the contents described in the following examples, and it goes without saying that the present invention may be carried out with modifications within a scope suitable for the present invention.
In the following examples, SnO is used2Powder and ZnO powder. In addition, in the case of adding an additive element, as the additive element Ta, Ta is used2O5Powder of GeO as an additive element Ge2And (3) pulverizing.
(example 1)
In example 1, a sputtering target (made of sumitomo metal mine) was produced using a sintered body produced so that zinc oxide was used as a main component and tin oxide was 0.26 in terms of a metal atomic ratio Sn/(Zn + Sn), and a sintered body produced so that tin oxide was 0.49 in terms of a metal atomic ratio Sn/(Zn + Sn). A DC magnetron sputtering apparatus (SH-550 model, manufactured by ULVAC) was used as the sputtering apparatus.
The deposition of the amorphous oxide sputtering film was performed under the following conditions. The target was attached to the cathode, and the resin film substrate was disposed directly above the cathode. The distance between the target and the resin film substrate was set to 80 mm. The resin film substrate on which the film is formed is made to stand on the opposite surface of the cathode, and the film is formed on the stationary opposite side. A PEN film (manufactured by imperial, 50 μm thick) was used as the resin film substrate. The vacuum degree in the chamber reaches 2 x 10-4When the pressure is not more than Pa, argon gas having a purity of 99.9999 mass% is introduced into the chamber so that the pressure becomes 0.6Pa, a DC power supply (MDX, manufactured by DELTA.) is used as a DC power supply in argon gas containing 5% oxygen, a DC power of 1500W is applied between the sputtering target and the PEN film substrate by a DC pulse of 20kHz, plasma is generated by the DC pulse, and a 1 st oxide film having a metal atomic ratio Sn/(Zn + Sn) of 0.26 is formed on the PEN film substrate by sputtering to a film thickness of 50 nm. Next, a 2 nd oxide film was formed by sputtering so that the metal atomic ratio Sn/(Zn + Sn) of tin oxide was 0.49 at a film thickness of 50 nm.
The crystallinity, Water Vapor Transmission Rate (WVTR), and chemical resistance of the deposited oxide sputtered film were confirmed. Regarding the crystallinity, X-ray diffraction measurement was carried out, and a diffraction peak was observed, and the water vapor transmission rate was measured by a pressure difference method (DELTAPERM-UH manufactured by Technolox Co., Ltd.). The transmittance was measured with a spectrophotometer as the average transmittance of visible light at a wavelength of 550 nm. The chemical resistance was evaluated by immersing the sample in 5% hydrochloric acid or 5% aqueous sodium hydroxide for 5 minutes. The chemical temperature at this time is normal temperature. The samples before and after the chemical reagent immersion were measured by a spectrocolorimeter (Konika Meinenda, model: CM-5), and the color difference Δ Eab was calculated. In addition, regarding the amount of thickness reduction (film change amount) before and after the chemical reagent immersion, the amount of Zn and Sn dissolved in the chemical reagent immersed in the sample was confirmed by the ICP-AES method (ICPS-8100, Shimadzu corporation), and the film change amount was checked from the result, the film formation area, and the film density. In the chemical resistance evaluation, a substrate having a transparent oxide laminated film formed on a glass substrate is used in order to insolubilize the substrate. The results are shown in Table 1.
(example 2)
In example 2, a transparent oxide laminated film was obtained and measured in the same manner as in example 1 except that the 1 st oxide film was sputtered so that the metal atom ratio Sn/(Zn + Sn) was 0.18 and the metal atom ratio Sn/(Zn + Sn) of the 2 nd oxide film was 0.59. The results are shown in Table 1.
(example 3)
In example 3, a transparent oxide laminated film was obtained and measured in the same manner as in example 1, except that the 1 st oxide film was formed to have a film thickness of 70nm by sputtering, and the 2 nd oxide film having a metal atom ratio Sn/(Zn + Sn) of 0.68 was formed to have a film thickness of 20nm by sputtering. The results are shown in Table 1.
(example 4)
A transparent oxide laminated film was obtained and measured in the same manner as in example 1, except that in example 4, the 1 st oxide film was formed to have a film thickness of 15nm by sputtering, and the 2 nd oxide film was formed to have a film thickness of 15nm by sputtering. The results are shown in Table 1.
(example 5)
In example 5, a transparent oxide laminated film was obtained and measured in the same manner as in example 1 except that the 1 st oxide film having a metal atom number ratio of Sn/(Zn + Sn) of 0.22 was formed by sputtering at a film thickness of 15nm and the 2 nd oxide film having a metal atom number ratio of Sn/(Zn + Sn) of 0.59 was formed by sputtering at a film thickness of 15 nm. The results are shown in Table 1.
(example 6)
In example 6, a transparent oxide laminated film was obtained and measured in the same manner as in example 1, except that the 1 st oxide film was formed by sputtering to have a film thickness of 20nm, and the 2 nd oxide film having a metal atom ratio Sn/(Zn + Sn) of 0.68 was formed by sputtering to have a film thickness of 10 nm. The results are shown in Table 1.
(example 7)
In example 7, a transparent oxide laminated film was obtained and measured in the same manner as in example 1 except that the 1 st oxide film having a metal atom ratio Sn/(Zn + Sn) of 0.22, Ta/(Zn + Sn + Ge + Ta) of 0.01, and Ge/(Zn + Sn + Ge + Ta) of 0.04 was formed by sputtering in a film thickness of 30nm, and the 2 nd oxide film was formed in a film thickness of 20 nm. The results are shown in Table 1.
(example 8)
In example 8, a transparent oxide laminated film was obtained in the same manner as in example 1 except that a 1 st oxide film having a metal atom ratio of Sn/(Zn + Sn) of 0.18 was formed by sputtering at a film thickness of 85nm, and a 2 nd oxide film having a metal atom ratio of Sn/(Zn + Sn), Ta/(Zn + Sn + Ge + Ta) of 0.79, Ge/(Zn + Sn + Ge + Ta) of 0.01, and Ge/(Zn + Sn + Ge + Ta) of 0.04 was formed by sputtering at a film thickness of 15nm, and measurement was performed. The results are shown in Table 1.
(example 9)
In example 9, a transparent oxide laminated film was obtained in the same manner as in example 1 except that a 1 st oxide film having a metal atomic ratio Sn/(Zn + Sn) of 0.28, Ta/(Zn + Sn + Ge + Ta) of 0.01, and Ge/(Zn + Sn + Ge + Ta) of 0.04 was formed by sputtering, and a 2 nd oxide film having a metal atomic ratio Sn/(Zn + Sn) of 0.68, Ta/(Zn + Sn + Ge + Ta) of 0.01, and Ge/(Zn + Sn + Ge + Ta) of 0.04 was formed by sputtering, and the measurement was performed. The results are shown in Table 1.
Comparative example 1
A transparent oxide laminated film was obtained and measured in the same manner as in example 1, except that in comparative example 1, the 1 st oxide film having a metal atom ratio Sn/(Zn + Sn) of 0.18 was formed by sputtering, and the 2 nd oxide film having a metal atom ratio Sn/(Zn + Sn) of 0.29 was formed by sputtering. The results are shown in Table 1.
Comparative example 2
A transparent oxide laminated film was obtained and measured in the same manner as in example 1, except that in comparative example 2, the 1 st oxide film having a metal atom ratio Sn/(Zn + Sn) of 0.16 was formed by sputtering, and the 2 nd oxide film having a metal atom ratio Sn/(Zn + Sn) of 0.49 was formed by sputtering. The results are shown in Table 1.
Comparative example 3
In comparative example 3, a transparent oxide laminated film was obtained in the same manner as in example 1 except that the 1 st oxide film having a metal atom ratio of Sn/(Zn + Sn) of 0.35 was formed by sputtering at a film thickness of 15nm, and the 2 nd oxide film having a metal atom ratio of Sn/(Zn + Sn), Ta/(Zn + Sn + Ge + Ta) of 0.79, Ge/(Zn + Sn + Ge + Ta) of 0.01, and Ge/(Zn + Sn + Ge + Ta) of 0.04 was formed by sputtering at a film thickness of 15nm, and measurement was performed. The results are shown in Table 1.
[ Table 1]
Figure BDA0002685601210000161
As can be seen from Table 1: in examples 1 to 9 included in the present invention, the water vapor transmission rate obtained by the prescribed pressure difference method in accordance with the K7129 method of JIS standards was 0.001g/m2Less than/day (1.0X 10)-3g/m2Below/day) has good water vapor barrier properties. Further, the color difference Δ Eab in the evaluation of chemical resistance was 1.0 or less, and the film change amount was 2.0nm or less, and it was found that the film had good chemical resistance.
On the other hand, in comparative example 1 in which Sn/(Zn + Sn) of the 2 nd oxide film was 0.29, the transparent oxide laminated film was dissolved in an acid or an alkali in the chemical resistance evaluation.
In comparative example 2 in which Sn/(Zn + Sn) of the 1 st oxide film was 0.16 and comparative example 3 in which Sn/(Zn + Sn) of the 1 st oxide film was 0.35, the water vapor transmission rate obtained by the prescribed differential pressure method in accordance with K7129 method of JIS standards exceeded 0.001g/m 2/day(1.0×10-3g/m2And day), it was found that the water vapor barrier property was poor. In addition, at wavelength 550nThe transmittance measured at m was also 90% or more, and it was found that the film had transparency. In addition, as for crystallinity, X-ray diffraction measurement was performed, and as a result, it was amorphous in all of examples 1 to 9.
As described above, according to the present invention, a transparent oxide laminated film having excellent transparency, good water vapor barrier performance, and chemical resistance can be obtained by dc sputtering with high mass productivity.
Although one embodiment and each example of the present invention have been described in detail as above, it is easily understood by those skilled in the art that many modifications can be made without substantially departing from the novel matters and effects of the present invention. Therefore, all such modifications are included in the scope of the present invention.
For example, in the specification or the drawings, a term described at least once with a broader or synonymous but different term may be replaced with a different term in any part of the specification or the drawings. The transparent oxide laminated film, the method for producing the transparent oxide laminated film, and the structure of the transparent resin substrate are not limited to the description of one embodiment of the present invention and the examples, and various modifications can be made.
Industrial applicability
The transparent oxide laminated film according to the present invention can be used to form a water vapor barrier transparent resin substrate, and by using the water vapor barrier transparent resin substrate, a liquid crystal display element, an electroluminescence display element (EL display element), a quantum dot display element (QD display element), an electronic paper, a film-type solar cell, and the like having a degree of freedom in shape, curved surface display, and the like can be produced. Therefore, the present invention is extremely valuable in industry.

Claims (10)

1. A transparent oxide laminated film in which a plurality of transparent oxide films containing Zn and Sn are laminated,
the transparent oxide laminated film is composed of amorphous transparent oxide films having different metal atom ratios of Zn and Sn in each layer.
2. The transparent oxide laminated film according to claim 1, which comprises at least a 1 st transparent oxide film having a metal atom ratio of Sn/(Zn + Sn) of 0.18 to 0.29 inclusive, and a 2 nd transparent oxide film having a metal atom ratio of Sn/(Zn + Sn) of 0.44 to 0.90 inclusive.
3. The transparent oxide laminated film according to claim 2, wherein the transparent oxide film of at least one of the layers comprises Ta and Ge,
in the atomic ratio of Zn, Sn, Ta and Ge,
Ta/(Zn + Sn + Ge + Ta) is 0.01 or less, and Ge/(Zn + Sn + Ge + Ta) is 0.04 or less.
4. The transparent oxide laminate film according to claim 2, wherein the film thickness of the transparent oxide laminate film is 100nm or less.
5. The transparent oxide laminated film according to claim 2, which has a water vapor transmission rate of 0.001g/m in accordance with K7129 method of JIS standards and by a prescribed pressure difference method2And/day is less.
6. The transparent oxide laminated film according to claim 2, which has chemical resistance to an acid or an alkali, and has a color difference Δ Eab change value of 1.0 or less before and after immersion in a 5% hydrochloric acid solution or a 5% sodium hydroxide solution for 5 minutes.
7. The transparent oxide laminated film according to claim 2, which has chemical resistance to an acid or an alkali, and has a film change amount of 2.0nm or less before and after immersion in 5% hydrochloric acid or 5% sodium hydroxide solution for 5 minutes.
8. A method for producing a transparent oxide laminated film by sputtering using a target comprising a sintered Sn-Zn-O oxide,
a transparent oxide laminated film is formed by using at least a 1 st target and a 2 nd target, wherein the 1 st target has an oxide sintered body with Sn/(Zn + Sn) being 0.18 to 0.29 in terms of metal atom ratio, and the 2 nd target has an oxide sintered body with Sn/(Zn + Sn) being 0.44 to 0.90 in terms of metal atom ratio.
9. A transparent resin substrate obtained by forming the transparent oxide laminated film according to any one of claims 1 to 7 on at least one surface of a transparent resin base material.
10. The transparent resin substrate according to claim 9, wherein a transparent oxide film having Sn/(Zn + Sn) of 0.44 to 0.90 in terms of a metal atom number ratio is an outermost layer.
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