CN111954726A - Transparent oxide laminated film, method for producing transparent oxide laminated film, sputtering target, and transparent resin substrate - Google Patents

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

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Publication number
CN111954726A
CN111954726A CN201980025233.8A CN201980025233A CN111954726A CN 111954726 A CN111954726 A CN 111954726A CN 201980025233 A CN201980025233 A CN 201980025233A CN 111954726 A CN111954726 A CN 111954726A
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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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • 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
    • 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
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. 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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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

A transparent oxide laminated film having excellent transparency and good water vapor barrier performance or oxygen barrier performance, a method for producing the transparent oxide laminated film, a sputtering target, and a transparent resin substrate are provided by DC sputtering having high mass productivity. A transparent oxide laminated film obtained by laminating a plurality of transparent oxide films containing Zn and Sn has an amorphous film in which the metal atomic number ratio Sn/(Zn + Sn) of Zn to Sn is not less than 2 layers and not more than 0.18 and not more than 0.29.

Description

Transparent oxide laminated film, method for producing transparent oxide laminated film, sputtering target, and transparent resin substrate
Technical Field
The present invention relates to an amorphous transparent oxide laminated film containing Zn and Sn, a method for producing the same, a sputtering target used for forming the transparent oxide laminated film, and a transparent resin substrate having a transparent oxide laminated film formed on a base material. The present application claims priority based on japanese patent application No. 2018 @ -078442, filed in japan on day 16/4/2018, which is incorporated by reference into the present application.
Background
Resin substrates, which are formed by coating the surface of a transparent plastic substrate, a film substrate, or the like with a metal oxide film such as silicon oxide or aluminum oxide, are used for packaging purposes for the purpose of preventing the intrusion of water vapor or oxygen and preventing the degradation of foods, medicines, and the like. In recent years, the organic EL display device is also used for a liquid crystal display element, a solar cell, an electroluminescence display element (EL element), a Quantum Dot (QD) display element, a quantum dot sheet (QD sheet), and the like.
In recent years, as the development of display devices, transparent resin substrates having water vapor barrier properties and oxygen barrier properties used in electronic devices, particularly display devices, have been required to have not only light weight and large size but also flexibility in shape freedom, curved surface display, and the like. It is difficult to cope with the use of a glass substrate which has been used so far, and a transparent resin substrate has been used.
However, the base material of the transparent resin substrate is inferior to the base material of the glass substrate in water vapor barrier performance and oxygen barrier performance, and therefore, water vapor, oxygen, or the like penetrates the base material, and there is a problem that the EL display element, the QD display element, or the like is deteriorated. In order to solve such problems, a transparent resin substrate having improved water vapor barrier performance or oxygen barrier performance by forming a metal oxide film on a base material of the transparent resin substrate has been developed.
Particularly, with the practical use of EL display elements and QD display elements, in the case of displays using them, for example, organic EL displays, the following problems are known: if water vapor or oxygen is mixed in the organic EL display element, moisture is generatedThe damage caused at the interface between the cathode layer and the organic layer by oxidation has a great influence, and peeling between the organic layer and the cathode portion and black spots of the non-light-emitting portion occur, resulting in significant performance degradation. The Water Vapor Transmission Rate (WVTR) required for the transparent resin substrate usable in these displays is said to be 0.01g/m2Less than day, preferably 0.005g/m2Less than one day, Oxygen Transmission Rate (OTR) of 0.1cc/m2A value of less than or equal to day/atm, preferably 0.05cc/m2Less than/day/atm. In addition, there are demands for such displays to be flexible, and there is often a demand for a transparent resin substrate having a water vapor barrier property or an oxygen barrier property to be thin. For example, the film thickness of the barrier film is required to be 100nm or less.
For example, patent document 1 proposes an inorganic gas barrier film formed by an atomic layer deposition film method. It is described that the film can realize a water vapor permeability of 5X 10 at 40 ℃ and 90% RH-4g/(m2Day) below. The film thickness is 25nm to 100 nm.
Patent document 2 proposes a barrier film having an organic film layer and a gas barrier layer, in which the gas barrier layer is formed by a plasma CVD method. The water vapor permeability at this time is described as being 0.005g/m at 40 ℃ and 90% RH2The day is less. The thickness of the gas barrier layer is 0.2 to 2 μm.
Patent document 3 describes a gas barrier transparent resin substrate (film) in which a tin oxide transparent conductive film is formed on a transparent resin substrate (film) by a sputtering method. Water vapor transmission rate less than 0.01g/m2The transparent resin substrate (thin film) used was 200 μm per day, and the thickness of the barrier film was 100 to 200 nm.
Patent document 4 describes a technique of providing a silicon oxynitride film on a resin film base material by a sputtering method.
Patent document 5 proposes a laminated high barrier thin film using fluorine, silicon oxide, aluminum oxide film, or the like. It is described that the oxygen transmission rate at this time is 0.5cc/m2Less than one day/atm, and a water vapor permeability of 0.5g/m2The day is less. This is achieved byThe thickness of the barrier layer is
Figure BDA0002719307730000021
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-121721
Patent document 2: japanese patent laid-open publication No. 2016-155241
Patent document 3: japanese patent laid-open publication No. 2005-103768
Patent document 4: japanese laid-open patent publication No. 2002-100469
Patent document 5: japanese patent No. 2892793
Disclosure of Invention
Problems to be solved by the invention
However, in the film forming method of patent document 1, the film thickness is thin and the water vapor permeability may be 0.005g/m2However, the atomic layer deposition method is a special apparatus, and an expensive apparatus must be purchased. Further, the film forming rate is also slow, the productivity is low, and the like, and for these reasons, the film forming method is not adopted in mass production. The plasma CVD method, which is the film formation method of patent document 2, has a high film formation rate, but the formed gas barrier film is likely to have a fluctuating film thickness and characteristics, and has low stability. The versatility is also poor. Furthermore, if the film thickness is as thick as 0.2 to 2 μm, the flexibility of the film is poor.
In addition, in patent document 3 using a sputtering method widely used in industry, the water vapor transmittance is measured by the MOCON method, but in the measurement by the MOCON method, it is difficult to accurately measure 0.01g/m2Values below/day, the water vapor barrier properties of practical films are questionable. Furthermore, the film has poor flexibility because the thickness of the film is 100 to 200 nm. In patent document 4, although a silicon nitride film has a gas barrier property better than a silicon oxide film and an aluminum oxide film, it is generally a colored film, and therefore, it cannot be used as a gas barrier film of a transparent resin substrate for display, which requires transparency. Further, even when a part of nitrogen in silicon nitride is replaced with oxygen and the film is rendered colorlessThe thickness is up to 200nm, and the flexibility is poor. Patent document 5 describes a film in which a plurality of films such as aluminum oxide are used and oxygen permeability and water vapor permeability are compatible with each other, but the film has not yet sufficient characteristics.
When a barrier film formed by a sputtering method widely used in industry is used as a barrier film used in an EL display element, a QD display element, or the like, high characteristics such as a thin film thickness and a good water vapor transmittance or oxygen transmittance are further required.
The present invention has been made in view of such a demand, and an object thereof is to provide a transparent oxide laminated film having excellent transparency and good water vapor barrier performance or oxygen barrier performance, a method for producing the transparent oxide laminated film, a sputtering target, and a transparent resin substrate, by using dc sputtering having high mass productivity.
Means for solving the problems
In view of the above problems, the present inventors have conducted extensive analyses of film compositions suitable for water vapor barrier performance or oxygen barrier performance, and focused on lamination of a plurality of such films, 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 transparent oxide films containing Zn and Sn are laminated in a plurality of layers, and the transparent oxide laminated film has an amorphous film in which the metal atomic ratio Sn/(Zn + Sn) of Zn to Sn is 0.18 to 0.29 inclusive in 2 or more layers.
According to one embodiment of the present invention, by setting the above composition range, a transparent oxide laminated film having a good water vapor barrier performance or oxygen barrier performance can be obtained, and by further laminating an amorphous transparent oxide film having the above composition range, the 2 nd layer can cover a defective portion which occurs when the 1 st layer is formed, and a transparent oxide laminated film having a water vapor barrier performance or oxygen barrier performance which is better than that of a single film can be obtained.
In this case, in one embodiment of the present invention, the thickness of the transparent oxide laminated film may be 100nm or less.
In this way, a transparent oxide laminated film excellent in flexibility can be provided.
In one aspect of the present invention, the following may be provided: the transparent oxide film of at least one of the layers contains Ta and Ge, and 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 thus the film formation rate is increased by improving the conductivity of the target itself, and the film formation can be stably performed by increasing the target density.
In one aspect of the present invention, the following may be provided: the water vapor permeability obtained by the pressure difference method specified by the K7129 method according to JIS standard is 0.0008g/m when the total film thickness of the transparent oxide laminated film is 50-100 nm2Less than or equal to 0.004g/m when the total film thickness of the transparent oxide laminated film is less than 50nm2The day is less.
By satisfying the above requirements, a transparent oxide laminated film having excellent water vapor barrier properties can be obtained.
In one aspect of the present invention, the following may be provided: the oxygen permeability obtained by a pressure difference method specified by the K7126 method according to JIS standard is 0.008cc/m when the total film thickness of the transparent oxide laminated film is 50 to 100nm2A total film thickness of the transparent oxide laminate film of less than 50nm of 0.04cc/m2Less than/day/atm.
By satisfying the above requirements, the transparent oxide laminated film having excellent oxygen barrier performance can be obtained.
Another aspect of the present invention is a sputtering target used for forming the transparent oxide laminated film by a sputtering method, the sputtering target comprising an Sn — Zn — O-based oxide sintered body, a bonding material, and a backing plate, wherein the metal atomic ratio Sn/(Zn + Sn) of Zn to Sn contained in the oxide sintered body is 0.18 to 0.29.
By sputtering using a sputtering target having such a composition, a transparent oxide laminated film having excellent water vapor barrier performance or oxygen barrier performance can be formed.
In this case, according to another aspect of the present invention, the following may be provided: the oxide sintered body of the sputtering target further contains Ta and Ge, and the metal atomic ratio of Ta to Zn, Sn, Ge, Ta/(Zn + Sn + Ge + Ta), and the metal atomic ratio of Ge to Zn, Sn, Ta, Ge/(Zn + Sn + Ge + Ta), are 0.01 or less.
In this way, the conductivity of the oxide sintered body of the sputtering target is improved, and the film formation rate is increased, and further, the sintering density of the oxide sintered body is increased, so that the film can be stably formed, and a transparent oxide laminated film having further excellent water vapor barrier performance or oxygen barrier performance can be formed.
Another 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, the target having an oxide sintered body in which Sn/(Zn + Sn) is 0.18 or more and 0.29 or less in terms of a metal atom ratio, and the transparent oxide laminated film having 2 or more amorphous films is formed by interrupting sputtering at least 1 time during film formation.
According to another aspect of the present invention, by forming the 1 st and 2 nd layers not continuously, but by forming an interval for blocking discharge 1 time to relax the film stress, and laminating the oxide films having the amorphous composition range, the 2 nd layer can cover the defective portion occurring when the 1 st layer is formed, and a transparent oxide laminated film having a water vapor barrier property or an oxygen barrier property better than that of a single film can be obtained.
In this case, in another embodiment of the present invention, the thickness of the transparent oxide laminated film may be 100nm or less.
In this way, a transparent oxide laminated film excellent in flexibility can be provided.
Another embodiment of the present invention is a transparent resin substrate in which the transparent oxide laminated film is formed on at least one surface of a transparent resin base material.
According to another aspect of the present invention, by forming the transparent oxide laminated film, a transparent resin substrate having excellent transparency and good water vapor barrier performance or oxygen barrier performance can be produced.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a transparent oxide laminated film having excellent transparency and good water vapor barrier performance or oxygen barrier performance, a method for producing the transparent oxide laminated film, a sputtering target, and a transparent resin substrate, by using dc sputtering having high mass productivity.
Detailed Description
The transparent oxide laminated film, the method for producing the transparent oxide laminated film, the sputtering target, and the transparent resin substrate according to the present invention will be described below in the following order. The present invention is not limited to the following examples, and may be modified as desired without departing from the spirit and scope of the present invention.
1. Transparent oxide laminated film
2. Sputtering target
3. Method for producing transparent oxide laminated film
4. 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, and the transparent oxide laminated film has an amorphous film in which the metal atomic ratio Sn/(Zn + Sn) of Zn to Sn is 0.18 to 0.29 in a range of 2 layers or more. By setting the composition range as described above, a transparent oxide laminated film having excellent water vapor barrier performance or oxygen barrier performance can be obtained, and by further laminating an amorphous transparent oxide film having the composition range described above, the 2 nd layer can cover a defective portion occurring at the time of film formation of the 1 st layer, and a transparent oxide laminated film having more excellent water vapor barrier performance or oxygen barrier performance than a single film can be obtained.
The transparent oxide laminated film according to one embodiment of the present invention is an oxide laminated film (oxide sputtering laminated film) formed by sputtering. The transparent oxide laminate film according to one embodiment of the present invention has water vapor barrier properties and oxygen barrier properties, and is used as a water vapor barrier film or an oxygen barrier film. Such a transparent oxide laminated film is used for the purpose of preventing deterioration by blocking water vapor and oxygen by covering the surface of a plastic substrate, a thin film substrate, for example, a flexible display element such as a liquid crystal display element, a solar cell, or an Electroluminescence (EL) display element as a metal oxide film by a sputtering method.
The transparent oxide laminated film according to one embodiment of the present invention is required to block water vapor and oxygen. For this reason, the barrier film is preferably as dense as possible, thin and uniform in thickness, and has few defects (gaps) through which moisture and oxygen pass. Therefore, the transparent oxide laminated film is formed by a sputtering method described later. The transparent oxide laminated film formed by this sputtering method is preferably amorphous as in patent document 3.
This is because, when the oxide film is a crystalline film, since grain boundaries exist in the film and water vapor and oxygen permeate through the grain boundaries, the water vapor barrier performance and the oxygen barrier performance are reduced. In addition, although the above patent document 3 proposes a tin oxide film as the amorphous film, when the tin oxide film is formed by a sputtering method, a target material constituting a sputtering target used for sputtering uses a tin oxide 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 there are many problems that stable film formation is not possible due to cracking of the target during sputtering. The transparent oxide laminated film according to one embodiment of the present invention is formed by using the Sn — Zn — O sputtering target described later, thereby eliminating the above-mentioned concerns.
That is, the transparent oxide laminated film according to one embodiment of the present invention is an amorphous transparent oxide laminated film having water vapor barrier performance or oxygen barrier performance, which contains 2 or more layers of Zn and Sn, and is characterized in that the metal atomic ratio Sn/(Zn + Sn) of Zn to Sn in each layer (for example, in the case of a 2-layer laminated film, the 1 st layer and the 2 nd layer) is 0.18 or more and 0.29 or less.
In this manner, when Sn/(Zn + Sn) is 0.18 or more and 0.29 or less in terms of the metal atom number ratio, good water vapor permeability or oxygen barrier performance can be obtained, and further, by laminating an amorphous transparent oxide film containing Zn and Sn of the same kind, better water vapor barrier performance or oxygen barrier performance can be obtained. Since a single film is formed continuously due to the sputtering characteristics, a defect portion once appears and remains even if the film thickness is increased. It is considered that by laminating the films, a defective portion which first appears in the 1 st layer can be complemented by the 2 nd layer which is newly formed. Further, by laminating amorphous transparent oxide films containing Zn and Sn of the same kind, extremely high adhesion can be obtained. Therefore, defects can be partially compensated, and a film which is as dense as a single layer can be obtained although it is laminated. The film thickness is not particularly limited, and is preferably uniform.
SnO when the metal atom number ratio Sn/(Zn + Sn) is less than 0.182The ratio is small, so that crystallinity is strong, ZnO is precipitated more, a partially crystallized portion (microcrystalline state) in the film increases, and the inflow of water vapor and oxygen from the grain boundary increases, and a transparent oxide laminated film having desired water vapor barrier performance or oxygen barrier performance cannot be obtained.
On the other hand, when the metal atom number ratio Sn/(Zn + Sn) is more than 0.29, SnO2The ratio increases, the stress of the film increases, and heat generated during film formation increases, and peeling of the film and damage to the substrate occur, so that a transparent oxide laminated film having water vapor barrier performance or oxygen barrier performance, which can be used for OLEDs, QDs, and the like, cannot be obtained.
Preferably, the transparent oxide laminated film according to one embodiment of the present invention further contains Ta and Ge, and the metal atomic ratio Ta/(Zn + Sn + Ge + Ta) of Ta to Zn, Sn, and Ge is 0.01 or less, and the metal atomic ratio Ge/(Zn + Sn + Ge + Ta) of Ge to Zn, Sn, and Ta is 0.04 or less.
Even if Ta or Ge is contained, the crystallization temperature is 600 ℃ or higher, and therefore an amorphous film structure can be easily obtained. Further, since the crystallization temperature is high, the amorphous state can be easily maintained even when there is an influence of heat during 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. Details are as described later.
Sputtering using a target to which Ta and Ge were added had no effect on the formed oxide film (oxide sputtered film). For example, no influence of the water vapor permeability, the oxygen permeability, and the like was observed. Therefore, in the transparent oxide laminated film according to one embodiment of the present invention, even if Sn/(Zn + Sn) is 0.18 or more and 0.29 or less, Ta is 0.01 or less/(Zn + Sn + Ge + Ta), and Ge/(Zn + Sn + Ge + Ta) is 0.04 or less in terms of the metal atom number ratio, the water vapor barrier performance and the oxygen barrier performance do not deteriorate, and an amorphous transparent oxide laminated film having good characteristics can be obtained.
The total film thickness (the sum of the film thicknesses of the oxide films) of the transparent oxide laminated film according to one embodiment of the present invention is preferably 100nm or less. Thus, a transparent oxide laminated film having excellent water vapor barrier performance or oxygen barrier performance of 100nm or less and further excellent flexibility can be provided. The total film thickness is more preferably 90nm or less. The lower limit of the film thickness of the transparent oxide laminated film according to one embodiment of the present invention is 10 nm.
If the thickness of the transparent oxide laminated film is less than 10nm, the oxide film is too thin, and therefore, the film thickness of the transparent resin substrate described later is difficult to ensure the quality of the entire film, and water vapor or oxygen is likely to pass through the transparent resin substrate with a slight defect. On the other hand, if the thickness of the transparent oxide laminated film is large, flexibility is deteriorated. In view of productivity and cost, the film thickness is preferably 100nm or less, and more preferably 90nm or less. Therefore, when used at 10 to 100nm, the film is required to be flexible, lightweight, and thin, and is an optimum film thickness for use in equipment assembly and mass production.
In addition, in the transparent oxide laminated film according to one embodiment of the present invention, the water vapor transmittance obtained by the pressure difference method specified by the K7129 method in accordance with JIS standards is preferably 0.0008g/m when the total film thickness of the transparent oxide laminated film is 50 to 100nm2Less than one day, preferably 0.004g/m when the total film thickness of the transparent oxide laminated film is less than 50nm2The day is less.
If the water vapor transmission rate obtained by the pressure difference method specified in the K7129 method according to JIS standard is 0.01g/m2When the amount of moisture is larger than a predetermined value, the OLED display element and the QD display element are contaminated with water vapor, and the deterioration due to moisture is accelerated at the interface between the display element layers and the like in the OLED display element and the QD display element, and peeling occurs at an early stage, and therefore, the device is difficult to be used for a long time.
When the water vapor permeability is compared with that of a single film in which films are not laminated, Sn/(Zn + Sn) of the single film is 0.18 to 0.29In the oxide film of the lower range, it has been conventionally only 3X 10 at 100nm-3g/m2Day, but 3.0X 10 was achieved for the first time in the present invention-4g/m2Water vapor transmission rate per day. Further, it was 4.7X 10 at 50nm for a single film-3g/m2A day, by lamination, 8X 10-4g/m2A day; the single film is 8.5X 10 at 10nm-3g/m2A day, by lamination, 3.3X 10-3g/m2A day; the laminated film can obtain a good water vapor permeability more than a single film.
In addition, in the transparent oxide laminated film according to one embodiment of the present invention, the oxygen transmittance obtained by the pressure difference method specified by the K7126 method according to JIS standards is preferably 0.008cc/m when the total film thickness of the transparent oxide laminated film is 50 to 100nm2A total film thickness of the transparent oxide laminate film of less than 50nm, preferably 0.04cc/m2Less than/day/atm.
If the oxygen transmission rate obtained by the pressure difference method specified by the K7126 method according to JIS standard is 0.1cc/m2When the voltage is higher than a predetermined value,/day/atm, oxygen is mixed into the OLED display element and the QD display element, and the deterioration due to oxygen becomes rapid at the interface of the display element layer and the like inside, and peeling occurs at an early stage, and the device is difficult to be used for a long time.
In the case of comparing the oxygen transmission rate between a single film and a laminated film in which the films are not laminated, the oxygen transmission rate is also similar, and in an oxide film in which Sn/(Zn + Sn) of the single film is in the range of 0.18 to 0.29, only 3.5X 10 at 100nm has been achieved in the past-2cc/m2Day/atm, whereas the present invention for the first time realized 2.8X 10-3cc/m2Oxygen transmission rate/day/atm. Further, the thickness of the single film was 4.3X 10 at 50nm-2cc/m2A/day/atm of 8X 10 by lamination-3cc/m2(iv)/day/atm; the single film is 8.3X 10 at 10nm-2cc/m2A/day/atm, 3.4X 10 by lamination-2cc/m2(iv)/day/atm; as with the water vapor permeability, the laminated film can obtain a good oxygen permeability as compared with a single film.
As described above, the transparent oxide laminated film according to one embodiment of the present invention can have excellent transparency and good water vapor barrier performance or oxygen barrier performance.
<2 > sputtering target >
Next, a sputtering target used for forming the transparent oxide laminated film by a sputtering method will be described. A sputtering target according to one embodiment of the present invention is composed of a Sn-Zn-O-based oxide sintered body, a bonding material, and a backing plate.
The oxide sintered body is characterized in that the metal atomic ratio Sn/(Zn + Sn) of Zn to Sn contained in the oxide sintered body is 0.18 to 0.29. The characteristics of the oxide sintered body are continued in the formed oxide film (oxide sputtered film).
Therefore, when the metal atom number ratio Sn/(Zn + Sn) of Zn to Sn contained in the oxide sintered body is less than 0.18, SnO2The ratio decreases, the crystallinity becomes strong, the precipitation of ZnO increases, the partially crystallized portion (microcrystalline state) in the film increases, the inflow of water vapor and oxygen from the grain boundary increases, and a transparent oxide laminated film having desired water vapor barrier performance or oxygen barrier performance cannot be formed.
On the other hand, when the metal atom number ratio Sn/(Zn + Sn) is more than 0.29, SnO2The increase in the ratio increases the stress of the film, and further increases the heat generated during film formation, resulting in peeling of the film and damage to the substrate, and thus a transparent oxide laminated film having water vapor barrier properties and oxygen barrier properties, which can be used for OLEDs, QDs, and the like, cannot be formed.
Further, in the oxide sintered body composed of a composition of Sn — Zn alone, the conductivity may be insufficient and the resistivity value may be large. In this way, in sputtering, as the resistivity value increases, sputtering with a larger energy is required, and the film deposition rate cannot be increased. It is therefore necessary to reduce the electrical conductivity of the sintered body used in the target. In the oxide sintered body, Zn2SnO4、ZnO、SnO2Is a substance having poor conductivity, and thus the compound phase, ZnO or SnO can be controlled even if the mixing ratio is adjusted2The conductivity cannot be improved significantly by adjusting the amount of (A).
Therefore, a predetermined amount of Ta (tantalum) is preferably added. Ta to Zn and Zn in ZnO phase2SnO4Zn or Sn, SnO in phase2Since Sn in the phase is replaced by Sn and dissolved in the solution, a ZnO phase having a wurtzite crystal structure and Zn having a spinel crystal structure are not formed2SnO4SnO of phase and rutile type crystal structure2Compound phases other than the phase. By adding Ta, the conductivity is improved while maintaining the density of the oxide sintered body.
Further, the sintered density of the oxide sintered body composed of a composition of Sn — Zn alone is about 90%, which may be insufficient. If the density of the oxide sintered body is low, there is a problem that stable film formation is not possible due to cracking of the oxide sintered body during sputtering.
Therefore, a predetermined amount of Ge (germanium) is preferably added. Ge to Zn and Zn in ZnO phase in oxide sintered body2SnO4Zn or Sn, SnO in phase2Since Sn in the phase is replaced by Sn and dissolved in the solution, a ZnO phase having a wurtzite crystal structure and Zn having a spinel crystal structure are not formed2SnO4SnO of phase and rutile type crystal structure2Compound phases other than the phase. Addition of Ge has an effect of densifying the oxide sintered body. This enables the sintered density of the oxide sintered body to be higher.
Therefore, it is preferable that the oxide sintered body further contains Ta and Ge, and the metal atomic ratio Ta/(Zn + Sn + Ge + Ta) of Ta to Zn, Sn, Ge is 0.01 or less, and the metal atomic ratio Ge/(Zn + Sn + Ge + Ta) of Ge to Zn, Sn, Ta is 0.04 or less. About the lower limit of the effect obtained by adding Ta and Ge, Ta and Ge were both 0.0005 in terms of the metal atom ratio.
When the metal atomic ratio Ta/(Zn + Sn + Ge + Ta) of Ta to Zn, Sn, Ge is more than 0.01, another compound phase, for example, Ta2O5、ZnTa2O6And a compound phase, and therefore, the conductivity cannot be greatly improved. When the ratio of the metal atoms of Ge to Zn, Sn and Ta, Ge/(Zn + Sn + Ge + Ta), is more than 0.04, another compound is formedPhase, e.g. Zn2Ge3O8The density of the oxide sintered body is lowered by the compound phase, and the target is easily broken during sputtering.
The sputtering target according to one embodiment of the present invention is a specific target production method, which is not limited to the following. First, a Zn oxide powder, a Sn oxide powder, and, if necessary, an oxide powder containing an additive element of Ta and Ge are adjusted and mixed to form the above-described preferred metal atom ratio with respect to the oxide sintered body. Then, the granulated powder is put into pure water or ultrapure water, an organic binder, a dispersant, and an antifoaming agent and mixed.
Next, hard ZrO was charged in use2A bead mill or the like, which wet-pulverizes the raw material powder, and then mixes and stirs the pulverized raw material powder to obtain a slurry. The obtained slurry is sprayed and dried by a spray dryer or the like to obtain a granulated powder.
Then, the granulated powder was subjected to pressure molding to obtain a molded article. For removing voids between particles of the granulated powder, the pressure is, for example, 294MPa (3.0 ton/cm)2) The left and right pressures are used for pressure forming. The method of Press molding is not particularly limited, and for example, a Cold Isostatic Press (CIP) capable of filling the granulated powder into a rubber mold and applying a high pressure is preferably used.
Then, the molded body is fired to obtain an oxide sintered body. The molded body is fired at a predetermined temperature for a predetermined time at a predetermined temperature rise rate in a firing furnace to obtain an oxide sintered body. The firing is performed, for example, in an atmosphere in a firing furnace in the air. The temperature rise rate from 700 ℃ to a predetermined sintering temperature in the sintering furnace is preferably 0.3 to 1.0 ℃/min. This is because ZnO and SnO are promoted2、Zn2SnO4The diffusion of the compound improves the sinterability and the conductivity. By setting such a temperature rise rate, ZnO and Zn are suppressed in a high temperature region2SnO4The volatilization effect of (1).
When the temperature rise rate in the sintering furnace is less than 0.3 ℃/min, the diffusion of the compound is reduced. On the other hand, when the temperature is more than 1.0 ℃/min, the temperature rise rate is high, and therefore, the formation of the compound is incomplete, and a dense oxide sintered body cannot be produced.
The sintering temperature after the temperature rise is preferably 1300 ℃ to 1400 ℃. When the sintering temperature is lower than 1300 ℃, the temperature is too low, ZnO and SnO2、Zn2SnO4Grain boundary diffusion of sintering in the compound does not proceed. On the other hand, if the temperature exceeds 1400 ℃, grain boundary diffusion is promoted to progress sintering, but volatilization of the Zn component cannot be suppressed, and large pores remain in the oxide sintered body.
The holding time after the temperature rise is preferably 15 hours to 25 hours. When the holding time is less than 15 hours, sintering is incomplete, and therefore, a sintered body having large strain and warpage is obtained, and grain boundary diffusion does not proceed and sintering does not proceed. As a result, a dense sintered body cannot be produced. On the other hand, when the reaction time exceeds 25 hours, ZnO or Zn is present2SnO4The amount of (2) increases, resulting in a decrease in density of the oxide sintered body, deterioration in operation efficiency and high cost.
The sputtering target composed of the sintered oxide body produced as described above is produced, for example, by the following method. First, the oxide sintered body is mechanically polished to a desired size to obtain a processed body (target material). The obtained processed body is bonded (adhered) to a backing plate made of a copper material, a stainless steel material, or the like, using a bonding material such as indium (In), to obtain a sputtering target. The sputtering target may be formed by bonding a plurality of oxide sintered bodies. Further, instead of the flat plate-shaped sputtering target, a cylindrical sputtering target in which an oxide sintered body formed in a cylindrical shape is joined to a backing tube using a joining material such as indium may be used.
As described above, according to the sputtering target according to one embodiment of the present invention, the transparent oxide laminated film having excellent transparency and good water vapor barrier performance or oxygen barrier performance can be formed by dc sputtering with high mass productivity.
<3 > 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. A method for producing a transparent oxide laminated film according to one embodiment of the present invention is a method for obtaining an amorphous, transparent film containing Zn and Sn and having water vapor barrier performance or oxygen barrier performance by sputtering using an Sn — Zn — O oxide sintered body.
The transparent oxide laminated film is characterized by comprising an oxide sintered body, wherein the metal atomic ratio Sn/(Zn + Sn) of Zn to Sn contained in the oxide sintered body used in the sputtering is 0.18 to 0.29, and the sputtering is interrupted at least 1 time in the film formation to form a transparent oxide laminated film having 2 or more amorphous films. It should be noted that the technical meaning of the above range is as described above.
The thickness of the oxide sputtering laminated film is preferably 100nm or less, and more preferably 90nm or less, as the total thickness. In this way, a transparent oxide laminated film having good water vapor barrier properties or oxygen barrier properties and more excellent flexibility can be provided.
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. The atmosphere in the chamber is inert gas. The inert gas is argon gas or the like, and the purity is preferably 99.999 mass% or more. In addition, the inert gas contains 4 to 10 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 form a predetermined resistance value. Then, a predetermined dc power supply was applied between the sputtering target and the base material, and plasma was generated by a dc pulse to perform sputtering and film formation, thereby obtaining a layer 1. Then, the mask gate was closed to interrupt the film formation for 1 time, and then the mask gate was opened again to form a film under the same conditions, thereby forming a 2 nd layer. By interrupting the discharge once and at a certain interval, canThe film stress can be reduced. In the case of an apparatus that continuously performs sputtering by the RTR method, the film can be formed by sputtering the 1 st layer and winding it, and then reversing it and sputtering the 2 nd layer. The film thickness is controlled by the film formation time.
By providing an interval for interrupting discharge 1 time without continuously forming the 1 st and 2 nd layers in this way, the film stress is also relaxed, and by laminating oxide films in the above-described composition range of amorphous, the 2 nd layer can be made to cover the defective portion occurring when the 1 st layer is formed.
The water vapor barrier property or the oxygen barrier property or the like of the transparent oxide laminated film can be obtained without greatly depending on the sputtering conditions. Even when the conditions are adjusted based on the required transmittance and resistance value, a film having good water vapor barrier performance or oxygen barrier performance can be easily produced.
As described above, according to the method for producing a transparent oxide laminated film according to one embodiment of the present invention, a transparent oxide laminated film having excellent transparency, and good water vapor barrier performance or oxygen barrier performance can be obtained by dc sputtering with high mass productivity.
<4 > transparent resin substrate
The transparent resin substrate according to one embodiment of the present invention is a transparent substrate on which the above-described transparent oxide laminated film containing Zn and Sn and having a water vapor barrier property or an oxygen barrier property is formed in an amorphous state. That is, the transparent oxide laminated film is formed on at least one surface of the substrate, and 2 or more oxide layers in which the metal atomic ratio Sn/(Zn + Sn) of Zn to Sn is 0.18 to 0.29 are formed. 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 view of flexibility, cost, and equipment requirements.
As a method of sputtering the transparent resin substrate, sputtering may be performed as described in the method of manufacturing the 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 a member in which an amorphous transparent oxide sputtering laminated film having water vapor barrier performance or oxygen barrier performance containing Zn and Sn is formed on at least one surface of the base material, and may be laminated with another film interposed therebetween. For example, for the purpose of surface planarization, improvement of optical characteristics, or the like, 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 transparent oxide laminated film may be formed as a water vapor barrier layer or an oxygen barrier layer on at least one of the substrates.
The transparent resin substrate according to one embodiment of the present invention can be used to form, for example, a flexible OLED display element, a flexible QD display element, and a QD sheet, which are one type of flexible display elements.
As described above, the transparent resin substrate according to one embodiment of the present invention has excellent transparency, and good water vapor barrier performance and oxygen barrier performance by dc sputtering with high mass productivity.
Examples
The present invention will be described in detail with reference to examples and 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 can be practiced with modification within a scope suitable for the present invention.
In the following examples and comparative examples, SnO was used2Powder and ZnO powder. In addition, in the case of adding an additive element, Ta is used as the additive element Ta2O5Powder of GeO as an additive element Ge2And (3) pulverizing.
(example 1)
In example 1, a sputtering target (manufactured by sumitomo metal mine) was produced using a sintered body produced so that zinc oxide was used as a main component and the metal atomic ratio Sn/(Zn + Sn) of tin oxide was 0.23, and a film was formed by sputtering using this sputtering target with a sputtering apparatus. A DC magnetron sputtering apparatus (SH-550 model, manufactured by ULVAC) was used as the sputtering apparatus.
The amorphous oxide film was formed 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 allowed to stand opposite to the cathode, and the film formation is performed so as to be stationary and opposed to each other. A PEN film (manufactured by Diziman, thickness: 50 μm) was used as the resin film substrate. The vacuum degree in the chamber reaches 2 x 10-4At a time of Pa or less, argon gas having a purity of 99.9999 mass% was introduced into the chamber to make a pressure of 0.6Pa, and in argon gas containing 5 volume% of oxygen, 1500W DC power using 20kHz DC pulse was applied between the sputtering target-made PEN film substrates using a DC power supply device (MDX, manufactured by DELTA) as a DC power supply, thereby generating plasma by DC pulse. On a PEN film substrate made of Dizier, an oxide sputtered film having a thickness of 50nm was formed as the 1 st layer by sputtering, the mask gate was closed, the film formation was interrupted once, the mask gate was opened again, and an oxide sputtered film having a thickness of 50nm was formed as the 2 nd layer by sputtering, thereby forming a transparent oxide laminated film having a total film thickness of 100 nm.
The crystallinity, Water Vapor Transmission Rate (WVTR), and Oxygen Transmission Rate (OTR) of the transparent oxide laminated film prepared as described above were confirmed. The crystallinity was measured by X-ray diffraction and the diffraction peak was observed; the water vapor permeability was measured by a pressure difference method (DELTAPERM-UH manufactured by Technolox Co., Ltd.). The oxygen transmission rate was also measured by a pressure difference method (GTR-2000X, manufactured by GTR technologies). The transmittance was measured with a spectrophotometer, assuming that the average transmittance of visible light at a wavelength of 550nm was used.
(example 2)
The transparent oxide laminated film according to example 2 was obtained in the same manner as in example 1, except that in example 2, a sumitomo metal mine sputtering target prepared so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.18 was used. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 3)
A transparent oxide laminated film according to example 3 was obtained in the same manner as in example 1, except that a sputtering target made of sumitomo metal mine, which was prepared so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.29, was used in example 3. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 4)
The transparent oxide laminated film according to example 4 was obtained in the same manner as in example 1 except that the sputtering target for sumitomo metal mine prepared so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.29 was used for the 1 st layer and the sputtering target for sumitomo metal mine prepared so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.18 was used for the 2 nd layer in example 4. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 5)
The transparent oxide laminated film according to example 5 was obtained in the same manner as in example 1 except that the sputtering target for sumitomo metal mine prepared so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.18 was used for the 1 st layer, and the sputtering target for sumitomo metal mine prepared so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.29 was used for the 2 nd layer in example 5. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 6)
In example 6, the transparent oxide laminated film according to example 6 was obtained in the same manner as in example 1 except that the oxide sputtered film with a thickness of 25nm was formed on the 1 st layer by sputtering, the mask gate was closed, the film formation was once interrupted, the mask gate was opened again, and the oxide sputtered film with a thickness of 25nm was formed as the 2 nd layer by sputtering, and the total film thickness was 50 nm. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 7)
In example 7, the transparent oxide laminated film according to example 7 was obtained in the same manner as in example 1 except that a sputtering target prepared in sumitomo metal mine and adjusted so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.18 was used, an oxide sputtered film having a thickness of 25nm was formed in the 1 st layer by sputtering, the barrier gate was closed, film formation was once interrupted, the barrier gate was opened again, and an oxide sputtered film having a thickness of 25nm was formed as the 2 nd layer by sputtering, and the total film thickness was 50 nm. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 8)
In example 8, the transparent oxide laminated film according to example 8 was obtained in the same manner as in example 1 except that a sputtering target prepared in sumitomo metal mine and adjusted so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.29, an oxide sputtered film having a thickness of 25nm was formed in the 1 st layer by sputtering, the barrier gate was closed, film formation was once interrupted, the barrier gate was opened again, and an oxide sputtered film having a thickness of 25nm was formed as the 2 nd layer by sputtering, and the total film thickness was 50 nm. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 9)
In example 9, the transparent oxide laminated film according to example 9 was obtained in the same manner as in example 1 except that the sputtering target for sumitomo metal mine, which was adjusted so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.29, was used for the 1 st layer, the sputtering target for sumitomo metal mine, which was adjusted so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.18, was used for the 2 nd layer, the oxide sputtered film with a thickness of 25nm was formed in the 1 st layer by sputtering, the mask gate was closed, the film formation was interrupted once, the mask gate was opened again, the oxide sputtered film with a thickness of 25nm was formed as the 2 nd layer by sputtering, and the total film thickness was 50 nm. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 10)
In example 10, the transparent oxide laminated film according to example 10 was obtained in the same manner as in example 1 except that the sputtering target for sumitomo metal mine, which was adjusted so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.18, was used for the 1 st layer, the sputtering target for sumitomo metal mine, which was adjusted so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.29, was used for the 2 nd layer, the oxide sputtered film with a thickness of 25nm was formed in the 1 st layer by sputtering, the mask gate was closed, the film formation was interrupted once, the mask gate was opened again, the oxide sputtered film with a thickness of 25nm was formed as the 2 nd layer by sputtering, and the total film thickness was 50 nm. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 11)
In example 11, a transparent oxide laminated film according to example 11 was obtained in the same manner as in example 1 except that an oxide sputtered film having a thickness of 5nm was formed on the 1 st layer by sputtering, the mask gate was closed, the film formation was once interrupted, the mask gate was opened again, and an oxide sputtered film having a thickness of 5nm was formed as the 2 nd layer by sputtering, and the total film thickness was set to 10 nm. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 12)
In example 12, the same operation as in example 1 was carried out except that a sputtering target prepared in sumitomo metal mine and adjusted so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.18 was used, an oxide sputtered film having a thickness of 5nm was formed on the 1 st layer by sputtering, the barrier gate was closed, the film formation was once interrupted, the barrier gate was opened again, and an oxide sputtered film having a thickness of 5nm was formed as the 2 nd layer by sputtering, and the total film thickness was 10nm, thereby obtaining a transparent oxide laminated film according to example 12. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 13)
In example 13, the same operation as in example 1 was carried out except that a sputtering target prepared in sumitomo metal mine and adjusted so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.29 was used, an oxide sputtered film having a thickness of 5nm was formed on the 1 st layer by sputtering, the barrier gate was closed, the film formation was once interrupted, the barrier gate was opened again, and an oxide sputtered film having a thickness of 5nm was formed as the 2 nd layer by sputtering, and the total film thickness was 10nm, thereby obtaining a transparent oxide laminated film according to example 13. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 14)
In example 14, the transparent oxide laminated film according to example 14 was obtained in the same manner as in example 1 except that the sputtering target for sumitomo metal mine was used for the layer 1 in which the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.29, the sputtering target for sumitomo metal mine was used for the layer 2 in which the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.18, the oxide sputtered film having a film thickness of 5nm was formed for the layer 1 by sputtering, the barrier gate was closed and the film formation was interrupted once, the barrier gate was opened again, and the oxide sputtered film having a film thickness of 5nm was formed as the layer 2 by sputtering, and the total film thickness was 10 nm. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 15)
In example 15, the transparent oxide laminated film according to example 15 was obtained in the same manner as in example 1 except that the sputtering target for sumitomo metal mine, which was adjusted so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.18, was used for the 1 st layer, the sputtering target for sumitomo metal mine, which was adjusted so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.29, was used for the 2 nd layer, the oxide sputtered film having a film thickness of 5nm was formed in the 1 st layer by sputtering, the shadow gate was closed, the film formation was interrupted once, the shadow gate was opened again, the oxide sputtered film having a film thickness of 5nm was formed as the 2 nd layer by sputtering, and the total film thickness was set to 10 nm. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 16)
In example 16, a sputtering target prepared for sumitomo metal mine was used in such a manner that the atomic ratio of Sn to Zn, Sn/(Zn + Sn), Ta/(Zn + Sn + Ge + Ta) was 0.23, the atomic ratio of Ge, Ge/(Zn + Sn + Ge + Ta) was 0.01, and the total film thickness was 100nm, in the same manner as in example 1, to obtain the transparent oxide laminated film according to example 16. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 17)
In example 17, a sputtering target prepared for sumitomo metal mine was used in such a manner that the atomic ratio of Sn to Zn, Sn/(Zn + Sn), Ta/(Zn + Sn + Ge + Ta) was 0.23, the atomic ratio of Ge, Ge/(Zn + Sn + Ge + Ta) was 0.01, and the total film thickness was 50nm, and the transparent oxide laminated film according to example 17 was obtained in the same manner as in example 6. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 18)
In example 18, a sputtering target prepared for sumitomo metal mine was used in such a manner that the atomic ratio of Sn to Zn, Sn/(Zn + Sn), Ta/(Zn + Sn + Ge + Ta) was 0.23, the atomic ratio of Ge, Ge/(Zn + Sn + Ge + Ta) was 0.01, and the total thickness was 10nm, and the transparent oxide laminated film according to example 18 was obtained in the same manner as in example 11. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 19)
In example 19, the transparent oxide laminated film according to example 19 was obtained in the same manner as in example 1 except that a sputtering target prepared in sumitomo metal mine, in which the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.23, was used, an oxide sputtered film having a film thickness of 45nm was formed on the 1 st layer of the PEN film substrate by sputtering, the formation of the film was interrupted once by closing the barrier gate, the barrier gate was opened again, and an oxide sputtered film having a film thickness of 45nm was formed as the 2 nd layer by sputtering, and the total film thickness was 90 nm. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 20)
In example 20, a transparent oxide laminated film according to example 20 was obtained in the same manner as in example 1, except that a sputtering target prepared in sumitomo metal mine, in which the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.18, was used, an oxide sputtered film having a film thickness of 20nm was formed on the 1 st layer of the PEN film substrate by sputtering, the film formation was interrupted once by closing the barrier gate, the barrier gate was opened again, and an oxide sputtered film having a film thickness of 20nm was formed as the 2 nd layer by sputtering, and the total film thickness was 40 nm. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 21)
In example 21, a transparent oxide laminated film according to example 21 was obtained in the same manner as in example 1, except that a sputtering target prepared in sumitomo metal mine, in which the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.29, was used, an oxide sputtered film having a film thickness of 20nm was formed on the 1 st layer of the PEN film substrate by sputtering, the formation of the film was interrupted once by closing the barrier gate, the barrier gate was opened again, and an oxide sputtered film having a film thickness of 20nm was formed as the 2 nd layer by sputtering, and the total film thickness was 40 nm. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 22)
The transparent oxide laminated film according to example 22 was obtained in the same manner as in example 6, except that in example 22, a substrate in which a SiON film having a thickness of 100nm was formed on a PEN film substrate made of imperial was used. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
(example 23)
In example 23, a 100nm thick SiO film was formed on a Dizimen PEN film substrate2A transparent oxide laminated film according to example 23 was obtained in the same manner as in example 6, except for the difference in the film base material. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
Comparative example 1
A transparent oxide laminated film according to comparative example 1 was obtained in the same manner as in example 1, except that a sputtering target made of sumitomo metal mine, which was adjusted so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.15, was used in comparative example 1. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
Comparative example 2
A transparent oxide laminated film according to comparative example 2 was obtained in the same manner as in example 1, except that a sputtering target made of sumitomo metal mine, which was adjusted so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.30, was used in comparative example 2. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
Comparative example 3
In comparative example 3, a transparent oxide laminated film according to comparative example 3 was obtained in the same manner as in example 1, except that a sputtering target prepared in sumitomo metal mine, in which the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.17, was used, that on the PEN film substrate made of imperial PEN, an oxide sputtered film having a film thickness of 2.5nm was formed on the 1 st layer by sputtering, the barrier gate was closed, the film formation was interrupted once, the barrier gate was opened again, an oxide sputtered film having a film thickness of 2.5nm was formed as the 2 nd layer by sputtering, and an oxide sputtered laminated film having a total film thickness of 5nm was sputtered. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
Comparative example 4
In comparative example 4, the transparent oxide laminated film according to comparative example 4 was obtained in the same manner as in example 1 except that the transparent oxide laminated film according to comparative example 4 was formed on the PEN film base material of sumitomo by using the sputtering target of sumitomo metal mine adjusted so that the atomic ratio Sn/(Zn + Sn) of Sn to Zn was 0.30, the oxide sputtered film having a film thickness of 2.5nm was formed on the 1 st layer by sputtering, the film formation was once interrupted by closing the barrier gate, the barrier gate was opened again, the oxide sputtered film having a film thickness of 2.5nm was formed as the 2 nd layer by sputtering, and the oxide sputtered laminated film having a total film thickness of 5nm was sputtered. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
Comparative example 5
In comparative example 5, a transparent oxide laminated film according to comparative example 5 was obtained in the same manner as in example 1, except that a sumitomo metal mine sputtering target prepared so that the atomic ratio of Sn to Zn, Sn/(Zn + Sn), was 0.18 was used and an oxide sputtered film having a film thickness of 100nm was sputtered as a single film on a PEN film substrate. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
Comparative example 6
In comparative example 6, a transparent oxide laminated film according to comparative example 6 was obtained in the same manner as in example 1, except that a sumitomo metal mine sputtering target prepared so that the atomic ratio of Sn to Zn, Sn/(Zn + Sn), was 0.23 was used and an oxide sputtered film having a thickness of 50nm as a single film was sputtered on a PEN film substrate made of imperial PEN. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
Comparative example 7
In comparative example 7, a transparent oxide laminated film according to comparative example 7 was obtained in the same manner as in example 1, except that an oxide sputtered film having a film thickness of 10nm was sputtered as a single film on a PEN film substrate made of sumitomo metal mine prepared so that the atomic ratio of Sn to Zn, Sn/(Zn + Sn), was 0.29. Crystallinity, water vapor permeability, and oxygen permeability were confirmed in the same manner as in example 1.
The results of examples 1 to 15 are shown in Table 1, and the results of examples 16 to 23 and comparative examples 1 to 7 are shown in Table 2.
[ Table 1]
Figure BDA0002719307730000221
[ Table 2]
Figure BDA0002719307730000231
According to Table 1, in all the examples in which Sn/(Zn + Sn) is in the range of 0.18 to 0.29, the water vapor permeability obtained by the differential pressure method specified by the K7129 method in accordance with JIS standards is 0.0008g/m at 50 to 100nm2Less than one day, 0.004g/m at less than 50nm2Less than one day, the water vapor barrier property is judged to be excellent. Further, according to Table 1, in all the examples in which Sn/(Zn + Sn) is in the range of 0.18 to 0.29, K71 in accordance with JIS standards is usedThe oxygen permeability obtained by a differential pressure method specified by 26 method is 0.008cc/m when the total film thickness of the transparent oxide laminated film is 50 to 100nm2A total film thickness of the transparent oxide laminate film of less than 50nm of 0.04cc/m2Less than/day/atm, and is judged to have excellent oxygen barrier properties. Therefore, in all examples, the water vapor barrier property and the good oxygen barrier property were within the above ranges, and the good water vapor barrier property and the good oxygen barrier property were exhibited. The transmittance measured at a wavelength of 550nm was also 90% or more, and the film had transparency. In this way, a transparent oxide laminated film having the above-described properties and more excellent in flexibility is obtained.
Further, as shown in examples 16 to 18, even when a sputtering target prepared in such a manner that the atomic ratio of Ta/(Zn + Sn + Ge + Ta) was 0.01 and the atomic ratio of Ge/(Zn + Sn + Ge + Ta) was 0.04 was used, the water vapor transmittance and the oxygen transmittance were both good. In addition, as for crystallinity, all of examples 1 to 23 were amorphous as measured by X-ray diffraction.
On the other hand, in comparative examples 1 to 4 in which Sn/(Zn + Sn) is out of the range of 0.18 to 0.29, the water vapor barrier performance and the oxygen barrier performance are inferior to those of examples beyond the above numerical value range. In addition, in comparative examples 5 to 7 in which only 1 film was formed, the water vapor barrier performance and the oxygen barrier performance were inferior to those of examples, even if the above numerical ranges were exceeded.
As described above, according to the present invention, it is possible to provide a transparent oxide laminated film having excellent transparency and good water vapor barrier performance or oxygen barrier performance, a method for producing the transparent oxide laminated film, a sputtering target, and a transparent resin substrate, by using dc sputtering with high mass productivity.
While the embodiments and examples of the present invention have been described in detail, those skilled in the art will readily appreciate that many modifications are possible without materially departing from the novel teachings and advantages of this invention. Therefore, all such modifications are included in the scope of the present invention.
For example, in the specification or drawings, certain terms are described at least once with different terms that are broader or synonymous, and these terms may be replaced with the different terms at any position in the specification or drawings. The transparent oxide laminated film, the method for producing the transparent oxide laminated film, and the configurations of the sputtering target and the transparent resin substrate are not limited to the configurations described in the embodiments and examples of the present invention, and various modifications can be made.
Industrial applicability
In the present invention, a transparent conductive film substrate (such as a flexible display element) using an oxide sputtering laminated film having excellent transparency and good water vapor barrier performance or oxygen barrier performance by dc sputtering with high mass productivity and excellent water vapor barrier performance or oxygen barrier performance and bendability, a method for producing the oxide sputtering laminated film, and an oxide sintered body and a transparent resin substrate is extremely useful as a member such as an OLED display element, a QD display element, and a QD sheet.

Claims (10)

1. A transparent oxide laminated film in which a plurality of transparent oxide films containing Zn and Sn are laminated,
the amorphous film has 2 or more layers, wherein the metal atomic ratio Sn/(Zn + Sn) of Zn to Sn is 0.18 to 0.29.
2. The transparent oxide laminate film according to claim 1, wherein a film thickness of the transparent oxide laminate film is 100nm or less.
3. The transparent oxide laminate film according to claim 1,
the transparent oxide film of at least any one layer contains Ta and Ge,
the metal atomic ratio Ta/(Zn + Sn + Ge + Ta) of Ta to Zn, Sn and Ge is less than 0.01,
the metal atomic ratio of Ge to Zn, Sn and Ta, Ge/(Zn + Sn + Ge + Ta), is less than 0.04.
4. The transparent oxygen of claim 1The laminate film is characterized in that the water vapor transmittance obtained by the pressure difference method specified by the K7129 method according to JIS standard is 0.0008g/m when the total film thickness of the transparent oxide laminate film is 50-100 nm2Less than or equal to 0.004g/m when the total film thickness of the transparent oxide laminated film is less than 50nm2The day is less.
5. The transparent oxide laminate film according to claim 1, wherein the oxygen transmittance obtained by a pressure difference method specified by K7126 method in accordance with JIS standard is 0.008cc/m when the total film thickness of the transparent oxide laminate film is 50 to 100nm2A total film thickness of 0.04cc/m or less at a value of less than 50nm2Less than/day/atm.
6. A sputtering target used for forming the transparent oxide laminated film according to any one of claims 1 to 5 by a sputtering method,
comprises an Sn-Zn-O oxide sintered body, a bonding material and a backing plate,
the oxide sintered body contains Zn and Sn in a metal atomic ratio Sn/(Zn + Sn) of 0.18 to 0.29.
7. The sputtering target according to claim 6,
the oxide sintered body further contains Ta and Ge,
the metal atomic ratio Ta/(Zn + Sn + Ge + Ta) of Ta to Zn, Sn and Ge is less than 0.01,
the metal atomic ratio of Ge to Zn, Sn and Ta, Ge/(Zn + Sn + Ge + Ta), is less than 0.04.
8. A method for producing a transparent oxide laminated film by sputtering using a target comprising a Sn-Zn-O-based oxide sintered body,
the target has an oxide sintered body having Sn/(Zn + Sn) of 0.18 to 0.29 in terms of a metal atom ratio,
by interrupting sputtering at least 1 time at the time of film formation, a transparent oxide laminated film having 2 or more amorphous films was formed.
9. The method of manufacturing a transparent oxide laminated film according to claim 8, wherein the film thickness of the transparent oxide laminated film is 100nm or less.
10. A transparent resin substrate having the transparent oxide laminate film according to any one of claims 1 to 5 formed on at least one surface of a transparent resin substrate.
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