TW201943554A - Transparent oxide laminate film, method for producing transparent oxide laminate film, sputtering target, and transparent resin substrate - Google Patents

Abstract

Provided are: a transparent oxide laminate film which can exhibit excellent transparency and good water vapor barrier performance or oxygen barrier performance in direct-current sputtering that is a technique having high mass productivity; a method for producing a transparent oxide laminate film; a sputtering target; and a transparent resin substrate. A transparent oxide laminate film which comprises multiple transparent oxide films containing Zn and Sn and laminated on each other, and which has at least two amorphous films each having a Zn/Sn metal atom number ratio, i.e., a Sn/(Zn+Sn) ratio, of 0.18 to 0.29 inclusive.

Description

Transparent oxide laminated film, method for manufacturing transparent oxide laminated film, sputtering target, and transparent resin substrate

The present invention relates to an amorphous transparent oxide laminated film containing Zn and Sn and a method for manufacturing the same. A sputtering target and a transparent oxide laminated film are used to form a transparent oxide laminated film. Transparent resin substrate on the substrate. This application is based in Japan, and was filed on April 16, 2018 with Japanese Patent Application No. Japanese Patent Application No. 2018-078442 as a basis for claiming priority. This application is hereby incorporated by reference.

A resin substrate coated with a metal oxide film such as silicon oxide or aluminum oxide on the surface of a transparent plastic substrate or film substrate is used to prevent the intrusion of water vapor and oxygen, and to prevent the deterioration of food or medicine. use. In recent years, liquid crystal display elements, solar cells, electroluminescent display elements (EL elements), quantum dot (QD) display elements, quantum dot sheets (QD sheets), etc. have also been used.

For transparent resin substrates used in electronic devices, especially display elements, which have water vapor barrier properties or oxygen barrier properties, in recent years, in accordance with the expansion of display elements, plus the requirements for weight reduction and large-scale, Requirements for flexibility of shape, flexibility of curved surface display, etc. Among the glass substrates used so far, the correspondence is strict, and transparent resin substrates have been used.

However, the base material of the transparent resin substrate is compared with the base material of the glass substrate. The water vapor barrier performance or oxygen barrier performance is poor, and water vapor or oxygen can pass through the substrate to make the EL display element. The problem of deterioration of QD display elements. In order to improve such a problem, development of a transparent resin substrate in which a metal oxide film is formed on a substrate of a transparent resin substrate to improve water vapor barrier performance or oxygen barrier performance is being carried out.

In particular, with the practical use of EL display elements or QD display elements, when using such displays, such as organic EL displays, it is known that when water vapor or oxygen is mixed into the organic EL display elements, the cathode layer and the The interface of the organic layer is greatly affected by damage by moisture or oxidation, and peeling between the organic layer and the cathode portion, or dark spots in the non-luminous portion occur, and the performance is significantly reduced. The water vapor transmission rate (WVTR) required for a transparent resin substrate that can be used for these displays is considered to be 0.01 g / m ² / day or less, ideally 0.005 g / m ² / day or less, and the oxygen transmission rate (OTR) system that 0.1cc / m ² / day / atm or less, desirably 0.05cc / m ² / day / atm or less. In addition, these displays have requirements for flexibility and the like, and many requests for thinning of transparent resin substrates having water vapor barrier properties or oxygen barrier properties are cited. For example, the thickness of the barrier film is required to be 100 nm or less.

For example, Patent Document 1 proposes an inorganic gas barrier film formed by an atomic layer deposition film method. Based on this, it is described that a water vapor transmission rate of 5 × 10 ^-4 g / (m ² ･ day) or less at 40 ° C. and 90% RH can be achieved. The film thickness is 25 nm to 100 nm.

In addition, Patent Document 2 proposes a barrier film having an organic film layer and a gas barrier layer and forming a gas barrier layer by a plasma CVD method. The water vapor transmission rate at this time is described as a water vapor transmission rate of 0.005 g / m ² / day or less at 40 ° C and 90% RH. The thickness of the gas barrier layer is 0.2 to 2 μm.

In addition, Patent Document 3 describes a gas barrier transparent resin substrate (thin film) having a transparent conductive film of tin oxide formed on a transparent resin substrate (thin film) by a sputtering method. The water vapor transmission rate is less than 0.01 g / m ² / day, the transparent resin substrate (thin film) used is 200 μm, and the film thickness of the barrier film is 100 to 200 nm.

In addition, Patent Document 4 describes that a silicon nitride oxide film is also applied to a resin film substrate by a sputtering method.

In addition, Patent Document 5 proposes a high barrier film using a layer of fluorine, silicon oxide, aluminum oxide film, or the like. It is described that the oxygen transmission rate at this time is 0.5 cc / m ² / day / atm or less, and the water vapor transmission rate is 0.5 g / m ² / day or less. The thickness of the barrier layer at this time is 200 to 1000 Å.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-121721
[Patent Document 2] Japanese Patent Laid-Open No. 2016-155241
[Patent Document 3] Japanese Patent Laid-Open No. 2005-103768
[Patent Document 4] Japanese Patent Laid-Open No. 2002-100469
[Patent Document 5] Japanese Patent No. 2892793

[Questions to be Solved by the Invention]

However, in the film forming method of Patent Document 1, although the film thickness can be made thin and the water vapor transmission rate is 0.005 g / m ² / day or less, the atomic layer deposition film method of the film forming method must be purchased with special equipment. Expensive device. In addition, for reasons such as a slow film formation speed and poor productivity, it has not been adopted for mass production systems. In the plasma CVD method of the film formation method of Patent Document 2, although the film formation speed is fast, the film thickness or characteristics of the gas barrier film to be formed are likely to be uneven, and the stability is low. Universality is also poor. The thickness of the film is 0.2 to 2 μm, which is not good for flexibility.

In Patent Document 3, which is widely used in industrial sputtering methods, the water vapor transmission rate is measured by the (isostatic method) MOCON method. However, in the measurement of the MOCON method, 0.01 g / m is accurately measured. Those below ² / day are difficult, but there is a problem with the actual water vapor barrier performance of the film. Furthermore, since the thickness of the film is 100 to 200 nm thick, it is not good in flexibility. In Patent Document 4, a silicon nitride film is superior to a silicon oxide film or an aluminum oxide film in terms of gas barrier performance, but in general, it is a colored film and cannot be used as a display that requires transparency. Gas barrier film for transparent resin substrate. In addition, when a part of the nitrogen of silicon nitride is replaced with oxygen to make it non-colored, the film thickness is 200 nm, which is not good in flexibility. Patent Document 5 describes a film that uses a plurality of films such as aluminum oxide and coexists with oxygen transmission rate and water vapor transmission rate, but the current situation is not sufficient.

As a barrier film used in EL display elements, QD display elements, etc., a film formed by a sputtering method widely used in the industry is required to have a thin film, and a good water vapor transmission rate or oxygen transmission rate is required. High characteristics.

Therefore, the present invention focuses on the structure of such a request, and its purpose is to provide: high-volume DC sputtering, excellent transparency, good transparency of water vapor barrier performance or oxygen barrier performance An oxide laminated film, a method for manufacturing a transparent oxide laminated film, a sputtering target and a transparent resin substrate.

Means to solve the problem

The present inventors have made an intensive analysis of the composition of the film suitable for the water vapor barrier performance or the oxygen barrier performance for the above-mentioned problems, and have focused on the multilayering of such films. As a result, they have completed to this invention.

That is, one aspect of the present invention is a transparent oxide multilayer film in which a transparent oxide film containing Zn and Sn is laminated, wherein Sn / (Zn + Sn) has a metal atomic ratio of Zn to Sn of two or more layers. An amorphous film of 0.18 to 0.29.

According to one aspect of the present invention, those who have the above-mentioned composition range have good water vapor barrier properties or oxygen barrier properties, and those who are laminated with the transparent oxide film of the above-mentioned composition range of amorphous, may A transparent oxide layered film having a second layer coating that is a defect portion that appears when the first layer is formed, and which has better water vapor barrier performance or oxygen barrier performance than a single film, can be obtained.

At this time, in one aspect of the present invention, the film thickness of the transparent oxide laminate film may be 100 nm or less.

By doing so, it is possible to provide a transparent oxide laminate film which is also superior in flexibility.

In one aspect of the present invention, at least one of the transparent oxide films contains Ta and Ge, and in the atomic ratio of Zn, Sn, Ta, and Ge, Ta / (Zn + Sn + Ge + Ta) It may be 0.01 or less, and Ge / (Zn + Sn + Ge + Ta) may be 0.04 or less.

Ta and Ge are components derived from the target. Through this, the film formation speed is improved by those who improve the conductivity of the target itself. In addition, those who increase the target density become stable and perform film formation.

In addition, in one aspect of the present invention, the water vapor transmission rate through the differential pressure method specified by the K7129 method in accordance with the JIS standard is 0.0008 g / for a total film thickness of the transparent oxide laminate film of 50 to 100 nm. m ² / day or less, and if the total film thickness of the transparent oxide laminate film is less than 50 nm, it can be regarded as 0.004 g / m ² / day or less.

By meeting the above requirements, it can be said that it is a transparent oxide laminated film with superior water vapor barrier properties.

In addition, in one aspect of the present invention, the oxygen transmission rate through the differential pressure method specified by the K7126 method in accordance with the JIS standard is 0.008cc / m in a total film thickness of the transparent oxide laminate film of 50 to 100 nm. ² / day / atm or less, and the total thickness of the transparent oxide laminate film is less than 50nm, it can be regarded as 0.04cc / m ² / day / atm or less.

When the above requirements are satisfied, it can be said that it is a transparent oxide laminate film having superior oxygen barrier properties.

Another aspect of the present invention is a sputtering target used for forming the transparent oxide layered film described above by a sputtering method, wherein the sputtering target is a sintered body of a Sn-Zn-O system and a bonding material. The back plate is configured, and the Sn / (Zn + Sn) ratio of the metal atomic ratio of Zn to Sn contained in the oxide sintered body is 0.18 or more and 0.29 or less.

When sputtering is performed using a sputtering target having such a composition, a transparent oxide laminated film having good water vapor barrier performance or oxygen barrier performance can be formed.

At this time, in other aspects of the present invention, the oxide sintering system of the sputtering target further contains Ta and Ge, and Ta / (Zn + Sn + Ge + Ta) in the metal atomic ratio of Ta to Zn, Sn, and Ge. It may be 0.01 or less, and Ge / (Zn + Sn + Ge + Ta) may be 0.04 or less as the ratio of the metal atomic ratio of Ge to Zn, Sn, and Ta.

In this way, the film formation speed is improved by improving the conductivity of the oxide sintered body of the sputtering target, and the film can be formed stably by the sintered density of the oxide sintered body, and the water having good water can be formed. A transparent oxide laminate film having vapor barrier properties or oxygen barrier properties is formed.

Another aspect of the present invention is a method for manufacturing a transparent oxide laminated film that is sputtered using a target made of a Sn-Zn-O oxide sintered body, wherein the target has a metal atomic ratio, Sn An oxide sintered body having a (Zn + Sn) of 0.18 or more and 0.29 or less forms a transparent oxide laminate film having two or more amorphous films when sputtering is interrupted at least once during film formation.

According to another aspect of the present invention, instead of continuously forming the first layer and the second layer, the film stress is relieved by being a spacer for interrupting one discharge, and by the oxidation in the above composition range of amorphous Those who laminate the material film can be covered by the second layer and become a defective part when forming the first layer, and a transparent oxide layer having better water vapor barrier performance or oxygen barrier performance than a single film can be obtained. Film.

In this case, in another aspect of the present invention, the thickness of the transparent oxide laminate film may be 100 nm or less.

By doing so, it is possible to provide a transparent oxide laminate film which is also superior in flexibility.

In another aspect of the present invention, the transparent oxide laminate film is a transparent resin substrate formed on at least one surface of a transparent resin substrate.

According to other forms, those who form the above-mentioned transparent oxide laminated film can be used as a transparent resin substrate having superior transparency, good water vapor barrier performance or oxygen barrier performance.

Invention effect

According to the present invention, it is possible to provide a transparent oxide layered film and a transparent oxide layered film with high productivity DC sputtering, superior transparency, good water vapor barrier performance or oxygen barrier performance. Manufacturing method, sputtering target and transparent resin substrate.

Hereinafter, the method for manufacturing a transparent oxide laminate film, a transparent oxide laminate film, a sputtering target, and a transparent resin substrate via the transparent oxide laminate film of the present invention will be described in the following order. However, the present invention is not limited to the following examples, and can be arbitrarily changed without departing from the scope of the present invention.
Transparent oxide laminated film
2.Sputter target
3. Manufacturing method of transparent oxide laminated film
4.Transparent resin substrate

＜ 1. Transparent oxide laminated film ＞
One aspect of the present invention is a transparent oxide laminate film in which a plurality of transparent oxide films containing Zn and Sn are laminated, wherein Sn / (Zn + Sn) having a metal atomic ratio of Zn to Sn of more than two layers is 0.18 An amorphous film of 0.29 or more. Those who have such a composition range have good water vapor barrier properties or oxygen barrier properties, and those who have an amorphous transparent oxide film of the above composition range can be covered by the second layer on the first layer. Defects that occur during the formation of a single layer become a transparent oxide laminate film with better water vapor barrier performance or oxygen barrier performance than a single film.

The transparent oxide layered film according to an embodiment of the present invention is an oxide layered film (oxide sputtered layered film) formed by sputtering. The transparent oxide laminate film according to an embodiment of the present invention has a water vapor barrier property and an oxygen barrier property, and is used as a water vapor barrier film or an oxygen barrier film. Such a transparent oxide laminated film is made of a flexible substrate or a thin film substrate, such as a liquid crystal display element or a solar cell, or an electroluminescent (EL) display element, which is prevented from being coated as a metal oxide film by a sputtering method. The surface of the display element is used for the purpose of blocking the deterioration of water vapor or oxygen.

The transparent oxide laminate film according to one embodiment of the present invention must block water vapor or oxygen. Therefore, it is preferable that the barrier film is as dense as possible, and the thickness is thin and uniform, and there are fewer defects (gap) through which moisture or oxygen passes. Therefore, the transparent oxide laminated film is formed by a sputtering method described later. The transparent oxide laminate film formed by the sputtering method is preferably one in which Patent Document 3 is amorphous.

This is the case where the oxide film is a crystalline film, and there is a grain boundary in this film. Water vapor or oxygen is transmitted through the grain boundary, and the water vapor barrier performance and oxygen barrier performance are reduced. In addition, in the above-mentioned Patent Document 3, a tin oxide-based film is proposed as this amorphous film. However, when a tin oxide-based film is formed by a sputtering method, it constitutes a sputtering target used for sputtering. The target material is a tin oxide system with the same composition as the film. Generally, the target material of the tin oxide system is high in acid resistance, but the relative density of the target material is low, and there are many problems such as that the target material cannot be formed stably through cracking during sputtering, etc. In the transparent oxide laminate film according to an embodiment of the present invention, those who have formed a film using a later-described Sn-Zn-O-based sputtering target have resolved the above-mentioned concerns.

That is, the transparent oxide laminate film according to an embodiment of the present invention is an amorphous transparent oxide laminate film having a water vapor barrier property and an oxygen barrier property including two or more layers of Zn and Sn. It is characterized in that each layer (for example, in the case of a two-layer laminated film, the first layer and the second layer) is Sn / (Zn + Sn) having a metal atomic ratio of Zn to Sn of 0.18 to 0.29.

In this way, if the metal atomic ratio is Sn / (Zn + Sn) as 0.18 or more and 0.29 or less, good water vapor transmission rate or oxygen barrier performance can be obtained, and the layer containing the same kind of Zn and Sn can be obtained. Those with an amorphous transparent oxide film can obtain better water vapor barrier performance or oxygen barrier performance. In the single film, the defect portion that appears once in the sputtering characteristics is formed continuously, and even if the film thickness is increased, it remains. In the case of a laminated film, a defect that appears in the first layer is considered to be a second layer that can be newly added. In addition, when an amorphous transparent oxide film containing the same kinds of Zn and Sn is laminated on each other, very high adhesion can be obtained. Therefore, it is possible to obtain a good and dense film, such as a single layer, while supplementing the defective portion while being laminated. There is no particular limitation on the thickness of each film, but it is desirable that the film thickness is uniform.

When the metal atomic ratio Sn / (Zn + Sn) is less than 0.18, the ratio of SnO ₂ decreases, and the precipitation of crystalline ZnO increases, and a part crystallized in the film (microcrystalline state). It increases, and water vapor or oxygen flows in from the grain boundary, 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 atomic ratio Sn / (Zn + Sn) is larger than 0.29, the larger the ratio of SnO ₂ is, the higher the stress of the film becomes, and the more the heat generated during film formation becomes larger. If there is peeling of the film or damage to the substrate, a transparent oxide laminated film having water vapor barrier performance or oxygen barrier performance which can be used for OLED, QD, etc. cannot be obtained.

The transparent oxide laminate film according to an embodiment of the present invention 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. The Ge / (Zn + Sn + Ge + Ta) ratio of the metal atomic ratio of Ge to Zn, Sn, and Ta is preferably 0.04 or less.

Even if Ta or Ge is contained, the crystallization temperature becomes 600 ° C or higher, and an amorphous film structure is easily obtained. In addition, the crystallization temperature is high, and even in the case of thermal influence in a mass production process, the amorphous state can be easily maintained. In addition, the addition of Ta and Ge at the above ratio has the effect of further improving the characteristics of a sputtering target containing Zn and Sn. The details are described later.

However, there is no influence on an oxide film (oxide sputtering film) formed by sputtering using a target to which Ta and Ge are added. For example, the influence of water vapor transmission rate and oxygen transmission rate was not recognized. Therefore, in the transparent oxide multilayer film according to an embodiment of the present invention, the Sn / (Zn + Sn) ratio is 0.18 or more and 0.29 or less in the metal atomic ratio, and Ta / (Zn + Sn + Ge + Ta) is 0.01 or less, and Ge / (Zn + Sn + Ge + Ta) is contained at a ratio of 0.04 or less. It does not deteriorate water vapor barrier performance or oxygen barrier performance, and has good characteristics. Those who obtained an amorphous transparent oxide laminated film.

The total film thickness (total film thickness of each oxide film) of the transparent oxide laminate film according to an embodiment of the present invention is preferably 100 nm or less. By doing so, it is possible to provide a transparent oxide laminate film which has good water vapor barrier performance or oxygen barrier performance below 100 nm and is more flexible. The total film thickness is more preferably 90 nm or less. The lower limit of the film thickness of the transparent oxide laminate film according to an embodiment of the present invention is 10 nm.

When the thickness of the transparent oxide laminated film becomes thinner than 10 nm, the oxide film becomes too thin, which makes it difficult to guarantee the quality of the entire thin film of the transparent resin substrate, which will be described later, and it is easy to cause slight defects. Pass water vapor or oxygen. On the other hand, if the thickness of the transparent oxide laminated film is thick, the flexibility is deteriorated. In view of productivity, the film thickness is preferably 100 nm or less, and more preferably 90 nm or less at cost. Therefore, when it is used at 10 to 100 nm, it meets the requirements of flexibility, weight reduction, and thin film. It is the best film thickness for use during device assembly or mass production.

In addition, in the transparent oxide laminate film according to one aspect of the present invention, the water vapor transmission rate of the transparent oxide laminate film according to the differential pressure method specified by the K7129 method according to the JIS standard is 50% in the total thickness of the transparent oxide laminate film. In ~ 100nm, it is preferably 0.0008g / m ² / day or less, and in a total oxide film thickness of less than 50nm, it is preferably 0.004g / m ² / day or less.

When the water vapor transmission rate is 0.01 g / m ² / day or more by the differential pressure method specified by the K7129 method according to the JIS standard, water vapor is mixed into the OLED display element or the QD display element, and the display element is internally The interface of the layer and the like is degraded early by the degradation of moisture, and peeling occurs at an early stage, which makes it difficult to use the device for a long time.

When the water vapor transmission rate is compared with a single film without a laminated film, the oxide film with a single film having Sn / (Zn + Sn) in the range of 0.18 or more and 0.29 or less can only reach 100 nm in the past. 3 × 10 ^-3 g / m ² / day, but for the first time in the present invention, a water vapor transmission rate of 3.0 × 10 ^-4 g / m ² / day is achieved. Furthermore, in a single film of 50 nm, 4.7 × 10 ^-3 g / m ² / day is used as a layerer. For 8 × 10 ^-4 g / m ² / day, in 10 nm, a single film is 8.5 × 10 ^-3 g / m ² / day, but it is 3.3 × 10 ^-3 g / m ² / day as a layerer. Compared with a single film, a laminated film can obtain a good water vapor transmission rate.

In addition, the transparent oxide laminate film according to an embodiment of the present invention has an oxygen transmission rate through a differential pressure method specified by the K7126 method according to JIS standards, and the total film thickness of the transparent oxide laminate film is 50. In ~ 100nm, it is preferably 0.008cc / m ² / day / atm or less, and in a total film thickness of the transparent oxide laminate film of less than 50nm, it is preferably 0.04cc / m ² / day / atm or less.

When the oxygen transmission rate through the differential pressure method specified by the K7126 method according to the JIS standard is 0.1cc / m ² / day / atm or more, an OLED display element or a QD display element is mixed with oxygen, and the internal display element is The interface of the layer and the like is deteriorated early by the degradation of oxygen, and peeling occurs at an early stage, which makes it difficult to use the device for a long time.

When comparing the oxygen transmission rate with a single film without a laminated film, even if it is an oxygen transmission rate, in an oxide film having a single film with Sn / (Zn + Sn) in the range of 0.18 or more and 0.29 or less, it was conventionally at 100 nm. It can only reach 3.5 × 10 ^-2 cc / m ² / day / atm, but for the first time in the present invention, it achieved an oxygen transmission rate of 2.8 × 10 ^-3 cc / m ² / day / atm. Moreover, in a single film of 50 nm, 4.3 × 10 ^-2 cc / m ² / day / atm is used as a layerer. For 8 × 10 ^-3 cc / m ² / day / atm, in 10 nm, a single film It is 8.3 × 10 ^-2 cc / m ² / day / atm, but it is 3.4 × 10 ^-2 cc / m ² / day / atm as a layerer, which is the same as the water vapor transmission rate and compared with the single film. , Laminated film can get good oxygen transmission rate.

From the above, the transparent oxide laminated film according to one embodiment of the present invention can have superior transparency, good water vapor barrier performance or oxygen barrier performance.

＜ 2. Sputtering target ＞
Next, a sputtering target used for forming the transparent oxide laminate film by a sputtering method will be described. A sputtering target according to an embodiment of the present invention is configured by a Sn-Zn-O-based oxide sintered body, a bonding material, and a backing plate.

The Sn / (Zn + Sn) ratio of the metal atomic ratio of Zn to Sn contained in the oxide sintered body is characterized by being 0.18 or more and 0.29 or less. The characteristics of the oxide sintered body continue to be the formed oxide film (oxide sputtering film).

Therefore, when the metal atomic ratio Sn / (Zn + Sn) of the Zn and Sn contained in the oxide sintered body is less than 0.18, the smaller the ratio of SnO ₂ is, the more crystalline ZnO is precipitated, and The part that crystallizes in the film (microcrystalline state) is increased, and the inflow of water vapor or oxygen from the grain boundaries increases, and the transparent oxide having the desired water vapor barrier performance or oxygen barrier performance cannot be obtained. A laminated film was formed.

On the other hand, when the metal atomic ratio Sn / (Zn + Sn) is larger than 0.29, the larger the ratio of SnO ₂ is, the higher the stress of the film becomes, and the more the heat generated during film formation becomes larger. If there is peeling of the film or damage to the substrate, it is impossible to form a transparent oxide laminated film having water vapor barrier performance or oxygen barrier performance for OLED, QD and the like.

In addition, in an oxide sintered body composed of only Sn—Zn, the conductivity may be insufficient, and the specific resistance may be large. In this type of sputtering, the larger the specific resistance value, the larger the energy must be used for sputtering, and the film formation speed cannot be increased. Therefore, it is necessary to reduce the conductivity of the sintered body used for the target. In the oxide sintered body, Zn ₂ SnO ₄ , ZnO, and SnO ₂ are substances that lack conductivity, and even if the compound phase or the amount of ZnO and SnO ₂ is adjusted as a mixing ratio, it cannot be significantly increased. Improved conductivity.

Therefore, it is preferable to increase Ta (tantalum) by a specific amount. Ta and Zn in the ZnO phase, Zn in the Zn ₂ SnO ₄ phase, or Sn in the SnO ₂ phase are substituted for solid solution, but no ZnO phase or spinel with wurtzite crystal structure is formed. Compound phases other than the Zn ₂ SnO ₄ phase with a stone-type crystal structure and the SnO ₂ phase with a rutile-type crystal structure. The addition of Ta maintains the density of the oxide sintered body and improves the conductivity.

In addition, the sintered density of the oxide sintered body composed of only the Sn—Zn composition is about 90%, and it may not be sufficient. When the density of the oxide sintered body is low, there is a problem such that the oxide sintered body is cracked during sputtering, and film formation cannot be performed stably.

Therefore, it is preferable to increase Ge (germanium) by a specific amount. Ge is in the oxide sintered body and replaces Zn in the ZnO phase, Zn in the Zn ₂ SnO ₄ phase, or Sn in the SnO ₂ phase to perform solid solution, but no wurtzite-type crystal is formed. A compound phase other than a ZnO phase having a structure, a Zn ₂ SnO ₄ phase having a spinel type crystal structure, and a SnO ₂ phase having a rutile type crystal structure. The addition of Ge has the effect of making the oxide sintered compact dense. As a result, the sintered density of the oxide sintered body can be made higher.

Accordingly, the above-mentioned oxide sintering system further contains Ta and Ge. Ta / (Zn + Sn + Ge + Ta) of the metal atomic ratio of Ta to Zn, Sn, and Ge is 0.01 or less, and the Ge and Ge / (Zn + Sn + Ge + Ta) with a metal atomic ratio of Zn, Sn, and Ta is preferably 0.04 or less. However, the approximate lower limit of the effect obtained by the addition of Ta and Ge is that at the same time as Ta and Ge, the metal atomic ratio is 0.0005.

The ratio of the metal atomic ratio of Ta to Zn, Sn, Ge above Ta / (Zn + Sn + Ge + Ta) is larger than 0.01, and other compound phases are generated, such as Ta ₂ O ₅ , ZnTa ₂ O ₆ and the like. Because of the compound phase, the conductivity cannot be greatly improved. In addition, the Ge / (Zn + Sn + Ge + Ta) ratio of the metal atomic ratio of Ge to Zn, Sn, and Ta is larger than 0.04, and another compound phase is generated, such as Zn ₂ Ge ₃ O ₈ Because of the compound phase, the density of the oxide sintered body becomes lower, and the target is easily broken during sputtering.

The sputtering target according to one embodiment of the present invention is not limited to the following, but a specific target manufacturing method is given. First, for oxide sintered bodies, oxide powders of Zn and Sn are required, and oxide powders containing Ta and Ge as additive elements are adjusted so as to have an ideal metal atomic ratio as described above. While mixed. The granulated powder described above is mixed with pure or ultrapure water, an organic binder, a dispersant, and an antifoaming agent.

Next, the raw material powder is wet-pulverized using a bead mill device or the like in which hard ZrO ₂ balls are put, and then mixed and stirred to obtain a slurry. A granulated powder can be obtained by spraying and drying the obtained slurry with a spray dryer device or the like.

Next, the above-mentioned granulated powder is pressure-molded to obtain a compact. In order to remove voids between the particles of the granulated powder, for example, press molding is performed at a pressure of about 294 MPa (3.0 ton / cm ² ). The method for press forming is not particularly limited, but for example, it is preferable to use a cold isostatic press (CIP: Cold Isostatic Press) method in which the above-mentioned granulated powder is filled in a rubber mold and a high pressure can be applied.

Next, the above-mentioned formed body is fired to obtain an oxide sintered body. The above-mentioned molded body is fired at a specific temperature rise rate in a firing furnace at a specific temperature and a specific time condition to obtain an oxide sintered body. The firing is performed, for example, in an atmosphere in a firing furnace in the atmosphere. The heating rate from 700 ° C to a specific sintering temperature in the sintering furnace is preferably a sintered molded body at a rate of 0.3 to 1.0 ° C / min. This is to promote the diffusion of ZnO, SnO ₂ or Zn ₂ SnO ₄ compounds, and to improve the sinterability, while also improving the conductivity. In addition, those having such a temperature increase rate have an effect of suppressing volatilization of ZnO or Zn ₂ SnO ₄ in a high temperature region.

When the temperature rise rate in the sintering furnace is less than 0.3 ° C / min, the diffusion of the compound is reduced. On the other hand, when the temperature exceeds 1.0 ° C / min, the temperature rise rate is fast, and the formation of the compound becomes incomplete, and a dense oxide sintered body cannot be produced.

The sintering temperature after heating is preferably 1300 ° C to 1400 ° C. When the sintering temperature is less than 1300 ° C, the temperature is too low, and the grain boundary diffusion of the sintering in the ZnO, SnO ₂ , and Zn ₂ SnO ₄ compounds cannot be developed. On the other hand, when it exceeds 1400 ° C, the grain boundary diffusion is promoted and the sintering system is developed, but the volatilization of the Zn component cannot be suppressed, and large voids remain inside the oxide sintered body.

The retention time after heating is preferably 15 hours to 25 hours. In the case where the holding time is less than 15 hours, the sintered body is deviated or bent due to incomplete sintering, while the grain boundary diffusion is not developed, and sintering cannot be performed. As a result, a dense sintered body cannot be produced. On the other hand, if it exceeds 25 hours, the volatilization of ZnO or Zn ₂ SnO ₄ increases, which results in a decrease in the density of the oxide sintered body, a deterioration in the work efficiency, and a high cost.

A sputtering target composed of the oxidized sintered body produced as described above is produced, for example, as follows. First, a machined body (target material) is obtained by subjecting the above-mentioned oxide sintered body to a mechanical grinding process to a desired size. A sputter target is obtained by bonding (joining) the obtained processed body to a back plate made of a copper material, a stainless steel material, or the like using a bonding material such as indium (In). The sputtering target may have a structure in which a plurality of laminated oxide sintered bodies are bonded. In addition to the plate-shaped sputtering target, a cylindrical oxide sintered body formed by joining a cylindrical oxide sintered body and a liner tube using a bonding material such as indium may be used.

From the above, according to the sputtering target according to one embodiment of the present invention, it can be a high-productivity DC sputtering, and it will have a transparent oxide with excellent transparency, good water vapor barrier performance or oxygen barrier performance. A laminated film is formed by a film.

<3. Manufacturing method of transparent oxide laminated film>
Next, a method for manufacturing a transparent oxide laminate film according to an embodiment of the present invention will be described. A method for manufacturing a transparent oxide laminate film according to an embodiment of the present invention is to use a Sn-Zn-O oxide sintered body and perform sputtering to obtain amorphous transparent water vapor containing Zn and Sn. Composition of a film having barrier properties or oxygen barrier properties.

In addition, an oxide sintered body having a Sn / (Zn + Sn) ratio of metal atomic ratio of Zn and Sn contained in the oxide sintered body used in the sputtering described above is 0.18 or more and 0.29 or less. When the sputtering is interrupted at least once during the film formation, a transparent oxide laminated film having an amorphous film of two or more layers is formed. However, the technical significance of the above range is as described above.

In addition, the film thickness of the above oxide sputtered laminated film is preferably 100 nm or less, and more preferably 90 nm or less. By doing so, it can provide a good water vapor barrier performance or oxygen barrier performance, and a transparent oxide laminate film which is superior in flexibility.

As the sputtering system, sputtering may be performed using a sputtering target composed of the above-mentioned oxide sintered body. The sputtering apparatus is not particularly limited, but a DC magnetron sputtering apparatus or the like can be used.

The sputtering conditions were such that the degree of vacuum in the processing chamber was adjusted to 1 × 10 ^-4 Pa or less. The environment in the processing room is the introduction of inert gas. An inert gas system, such as argon, and a purity of 99.999% by mass or more is preferred. In addition, the inert gas system contains 4 to 10% by volume of oxygen for the total gas flow rate. The oxygen concentration affects the surface resistance value of the film, and the oxygen concentration is set to a specific resistance value. Then, using a specific DC power supply, it was put between the sputtering target substrates, a plasma passing through a DC pulse was generated, and sputtering was performed to form a film to obtain a first layer. After that, the shutter was closed and the film formation was interrupted once, and then the shutter was opened again to perform film formation under the same conditions, and the second layer was formed into a film. If a certain interval is opened by one interrupted discharge, the film stress can be reduced. In addition, in the case of an RTR method, in the case of an apparatus that continuously performs sputtering, after the first layer is sputtered and wound, it is reversed and the second layer is sputtered to form a film. However, the film thickness is controlled by the film formation time.

In this way, instead of continuously forming the first layer and the second layer, the film stress is also reduced by the interval that interrupts one discharge, and then the oxide film of the above-mentioned composition range of the amorphous layer is laminated. In other words, it becomes a defective portion that can be formed when the second layer is coated on the first layer.

The water vapor barrier performance or oxygen barrier performance of the transparent oxide laminate film is obtained without depending on the sputtering conditions. Furthermore, in the case of adjusting the conditions according to the necessary transmittance and the state of the impedance value, it is also possible to easily produce a film having good water vapor barrier performance or oxygen barrier performance.

From the above, according to the method for manufacturing a transparent oxide laminate film according to an embodiment of the present invention, direct current sputtering with high productivity can be obtained, and excellent transparency, good water vapor barrier properties, or oxygen can be obtained. Barrier performance of transparent oxide laminated film.

<4. Transparent resin substrate>
A transparent resin substrate according to an embodiment of the present invention is a transparent oxide layered film having a transparent water vapor barrier property or an oxygen barrier property containing the above amorphous Zn and Sn, and is formed into a transparent film. Of the base material. That is, the transparent oxide laminate film is formed by forming two or more layers on at least one surface of the substrate, and the Sn / (Zn + Sn) ratio of the metal atomic ratio of Zn to Sn is 0.18 or more and 0.29 or less. Physical layer. The thickness of the transparent oxide laminated film is preferably 100 nm or less, and more preferably 90 nm or less.

As the transparent substrate, polyethylene terephthalate, polyethylene, naphthalenedicarboxylic acid, polycarbonate, polysulfonamide, polyether fluorene, polyaromatic ester, cycloolefin polymer, fluororesin, polypropylene can be used. , Polyimide resin, epoxy resin, etc. In addition, the thickness of the transparent resin substrate is not particularly limited, but in view of flexibility, cost, or device requirements, it is preferably 50 to 150 μm.

The sputtering method for the transparent resin substrate is as described in the method for manufacturing a transparent oxide laminated film, and the sputtering method may be performed. However, the above-mentioned technical significance of the optimal metal atomic ratio or film thickness of Zn to Sn is as described above.

In addition, a transparent resin substrate according to an embodiment of the present invention is formed on at least one surface of the substrate, and is oxidized to form an amorphous transparent water vapor barrier property or oxygen barrier property containing Zn and Sn. The structure of the object sputtering layered film is laminated, but it may be laminated with another film. For example, a silicon oxide film, a nitrided silicon oxide film, a resin film, a wet coating film, a metal film, an oxide film, etc. are formed on the above substrate for the purpose of flattening the surface or improving light characteristics. Then, as the water vapor barrier layer or the oxygen barrier layer, the transparent oxide laminate film may be formed on at least one of them.

A transparent resin substrate according to an embodiment of the present invention can be used to form, for example, a flexible OLED display element, a flexible QD display element, or a QD thin plate.

From the above, according to the transparent resin substrate according to one embodiment of the present invention, direct current sputtering with high mass productivity, excellent transparency, and good water vapor barrier performance or oxygen barrier performance can be obtained.

[Example]

Hereinafter, examples of the present invention will be specifically described with reference to comparative examples. However, the technical scope of the present invention is not limited to the description of the following examples, but it is of course also within the scope suitable for the present invention. , Plus the implementer of the change.

In the following examples and comparative examples, SnO ₂ powder and ZnO powder were used. In addition, in the case of adding an additive element, each of Ta ₂ O ₅ powder was used as the additive element Ta, and GeO ₂ powder was used as the additive element Ge.

(Example 1)
In Example 1, a sintered body produced using zinc oxide as the main component and tin oxide as the metal atomic ratio Sn / (Zn + Sn) to be 0.23 was used to produce a sputtering target (Sumitomo Metal Mines, Japan) (Manufactured), using this sputtering target, a film is formed by sputtering through a sputtering apparatus. This sputtering apparatus uses a DC magnetron sputtering apparatus (manufactured by ULVAC, SH-550 type).

The film formation of the amorphous oxide film is performed under the following conditions. A target is mounted on the cathode, and a resin film substrate is arranged directly above the cathode. The distance between the target and the resin film substrate was taken as 80 mm. The resin film base material on which the film is formed is caused to stand still on the opposite side of the cathode, and the film formation is performed on the stationary side. For the resin film substrate, a PEN film (made by Teijin, Japan, thickness: 50 μm) was used. When the degree of vacuum in the processing chamber reached 2 × 10 ^-4 Pa or less, 99.9999% by mass of argon gas was introduced into the processing chamber to have a gas pressure of 0.6Pa, and argon gas containing 5% by volume of oxygen was used as a DC power source. Using a DC power supply device (manufactured by DELTA, MDX), DC power of 1500 W using a DC pulse of 20 kHz was placed between the sputtering target and the Teijin PEN film substrate to generate a plasma passing through the DC pulse. On the Teijin PEN film substrate, as a first layer, an oxide sputtering film with a thickness of 50 nm was formed by sputtering, and the shutter was closed to interrupt the film formation once, and the shutter was opened again as the second layer. An oxide sputtering film having a thickness of 50 nm is formed by sputtering, and a transparent oxide laminated film having a total thickness of 100 nm is formed.

The crystallinity, water vapor transmission rate (WVTR), and oxygen transmission rate (OTR) of the transparent oxide laminate film prepared as described above were checked. The crystallinity was measured by X-ray diffraction, and the diffraction peak was observed. The water vapor transmission rate was measured by a differential pressure method (DELTAPERM-UH, manufactured by Technolox). The oxygen transmission rate was also measured by a differential pressure method (GTR-2000X manufactured by GTR TEC). The transmittance was measured with a spectrophotometer as the average transmittance of visible light at a wavelength of 550 nm.

(Example 2)
Example 2 was carried out in the same manner as in Example 1 except that a sputtering target made by Sumitomo Metal Mine of Japan was used in which the atomic ratio Sn / (Zn + Sn) of Sn and Zn was set to a ratio of 0.18. The transparent oxide laminated film of Example 2. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 3)
In Example 3, except that a sputtering target made by Sumitomo Metal Mine in Japan was used in which the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.29, the same procedure as in Example 1 was used. The transparent oxide laminated film of Example 3. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 4)
In Example 4, the first layer uses a sputtering target made of Sumitomo Metal Mine in Japan, where the atomic ratio of Sn and Zn Sn / (Zn + Sn) becomes 0.29, and the second layer uses Sn Except for the sputtering target made by Sumitomo Metal Mine in Japan, where the atomic ratio Zn of Sn / (Zn + Sn) is 0.18, a transparent oxide layer of Example 4 was obtained in the same manner as in Example 1. membrane. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 5)
In Example 5, the first layer uses a sputtering target made of Sumitomo Metal Mine in Japan, where the ratio of the atomic ratio of Sn and Zn Sn / (Zn + Sn) becomes 0.18, and the second layer uses Sn Except for the sputtering target made by Sumitomo Metal Mine, Japan, which has a ratio of Sn / (Zn + Sn) of 0.29 to a ratio of 0.29, it is the same as Example 1, and a transparent oxide layer of Example 5 is obtained. membrane. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 6)
In Example 6, an oxide sputtering film having a thickness of 25 nm was formed on the first layer by sputtering. The shutter was closed to interrupt the film formation once, and the shutter was opened again as the second layer through sputtering. Plating was carried out by forming an oxide sputtering film with a film thickness of 25 nm into a film to make a total film thickness of 50 nm. The same procedure as in Example 1 was performed to obtain a transparent oxide laminate film according to Example 6. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 7)
In Example 7, a sputtering target made of Sumitomo Metal Mine in Japan was used in which the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.18, and the film was deposited on the first layer by sputtering. An oxide sputtered film with a thickness of 25 nm is formed into the film. The shutter is closed to interrupt the film formation once, and the shutter is opened again. As a second layer, an oxide sputtered film with a thickness of 25 nm is formed into a film. Except for a film thickness of 50 nm, the same procedure as in Example 1 was performed to obtain a transparent oxide laminate film according to Example 7. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 8)
In Example 8, a sputtering target made of Sumitomo Metal Mine in Japan was used in which the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.29, and the film was deposited on the first layer by sputtering. An oxide sputtered film with a thickness of 25 nm is formed into the film. The shutter is closed to interrupt the film formation once, and the shutter is opened again. As a second layer, an oxide sputtered film with a thickness of 25 nm is formed into a film. Except for a film thickness of 50 nm, the same procedure as in Example 1 was performed to obtain a transparent oxide laminate film according to Example 8. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 9)
In Example 9, the first layer uses a sputtering target made by Sumitomo Metal Mine of Japan, which is a ratio of Sn / Zn atomic ratio Sn / (Zn + Sn) to 0.29, and is used in the second layer. The atomic ratio Sn / (Zn + Sn) of Sn and Zn is 0.18, and the sputtering target made by Sumitomo Metal Mine is blended. The first layer is formed by sputtering to form an oxide sputtering film with a thickness of 25 nm. Film, the shutter is closed to interrupt the film formation once, the shutter is opened again, and the second layer is formed by sputtering to form an oxide sputtering film with a film thickness of 25 nm to form a total film thickness other than 50 nm. Also in the same manner as in Example 1, a transparent oxide laminated film of Example 9 was obtained. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 10)
In Example 10, for the first layer, a sputtering target made of Sumitomo Metal Mine in Japan was used so that the atomic ratio of Sn and Zn Sn / (Zn + Sn) becomes 0.18. In the second layer, The atomic ratio Sn / (Zn + Sn) of Sn and Zn is 0.29, which is a sputtering target made of Sumitomo Metal Mine in Japan. The first layer is formed by sputtering to form an oxide sputtering film with a thickness of 25 nm. Film, the shutter is closed to interrupt the film formation once, and the shutter is opened again. As a second layer, an oxide film having a thickness of 25 nm is sputtered into the film to form a film. The total film thickness is 50 nm. In the same manner as in Example 1, a transparent oxide laminated film of Example 10 was obtained. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 11)
In Example 11, an oxide sputtering film having a thickness of 5 nm was formed on the first layer by sputtering, the shutter was closed to interrupt the film formation once, and the shutter was opened again as the second layer through sputtering. Plating was performed by forming an oxide sputtering film having a film thickness of 5 nm into a film to prepare a total film thickness of 10 nm. The same procedure as in Example 1 was performed to obtain a transparent oxide laminate film according to Example 11. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 12)
In Example 12, a sputtering target made of Sumitomo Metal Mine in Japan was used in which the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.18, and the film was deposited on the first layer by sputtering. An oxide sputtered film with a thickness of 5 nm is formed. The shutter is closed to interrupt the film formation once, and the shutter is opened again. As a second layer, an oxide sputtered film with a thickness of 5 nm is formed into a film. Except for a film thickness of 10 nm, the same procedure as in Example 1 was performed to obtain a transparent oxide laminate film according to Example 12. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 13)
In Example 13, a sputtering target made of Sumitomo Metal Mine of Japan was used in which the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.29, and the film was deposited on the first layer by sputtering. An oxide sputtered film with a thickness of 5 nm was formed into the film. The shutter was closed to interrupt the film formation once, and the shutter was opened again. As a second layer, an oxide sputtered film with a thickness of 5 nm was formed into the film. Except for a film thickness of 10 nm, the same procedure as in Example 1 was performed to obtain a transparent oxide laminate film according to Example 13. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 14)
In Example 14, the first layer uses a sputtering target made by Sumitomo Metal Mine of Japan, which is a ratio of Sn / Zn atomic ratio Sn / (Zn + Sn) to 0.29, and is used in the second layer. The atomic ratio Sn / (Zn + Sn) of Sn and Zn is a ratio of 0.18, which is a sputtering target made by Sumitomo Metal Mine of Japan. The first layer is formed by sputtering to form an oxide sputtering film with a thickness of 5 nm. Film, the shutter is closed to interrupt the film formation once, the shutter is opened again, and the second layer is formed by sputtering to form an oxide sputtering film with a film thickness of 5 nm, and the total film thickness is 10 nm. 1 In the same manner, a transparent oxide laminated film of Example 14 was obtained. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 15)
In Example 15, for the first layer, a sputtering target made of Sumitomo Metal Mine in Japan was used in which the atomic ratio of Sn and Zn Sn / (Zn + Sn) became 0.18. In the second layer, a sputtering target was used. The atomic ratio Sn / (Zn + Sn) of Sn and Zn is 0.29, and the sputtering target made by Sumitomo Metal Mine of Japan is blended. The first layer is formed by sputtering to form a 5 nm oxide sputtering film Film, the shutter is closed to interrupt the film formation once, and the shutter is opened again. As a second layer, an oxide film having a film thickness of 5 nm is sputtered into the film to form a film. The total film thickness is 10 nm. 1 In the same manner, a transparent oxide laminated film of Example 15 was obtained. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 16)
In Example 16, the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.23, the atomic number of Ta Ta / (Zn + Sn + Ge + Ta) was 0.01, and the atomic ratio of Ge Ge / (Zn + Sn + Ge + Ta) is a sputtering target made of Sumitomo Metal Mine, which is blended at a ratio of 0.04. As in Example 1, a transparent oxide layered film of Example 16 is obtained with a total film thickness of 100 nm. . The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 17)
In Example 17, a Sn / (Zn + Sn) atomic ratio Sn / (Zn + Sn) was 0.23, a Ta atomic number Ta / (Zn + Sn + Ge + Ta) was 0.01, and a Ge atomic ratio Ge / (Zn + Sn + Ge + Ta) is a 0.04 ratio sputtering target made by Sumitomo Metal Mine of Japan, which is the same as that of Example 6. As a result, a transparent oxide laminated film of Example 17 with a total film thickness of 50 nm is obtained. . The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 18)
In Example 18, the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.23, the atomic number of Ta Ta / (Zn + Sn + Ge + Ta) was 0.01, and the atomic ratio of Ge Ge / (Zn + Sn + Ge + Ta) is a sputtering target made of Sumitomo Metal Mine, which is blended at a ratio of 0.04, and is the same as in Example 11. As a result, a transparent oxide laminate film of Example 18 with a total film thickness of 10 nm is obtained . The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 19)
In Example 19, a sputtering target made by Sumitomo Metal Mine of Japan, which was blended so that the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.23, was used on a PEN thin film substrate made by Teijin. The first layer was formed by forming an oxide sputtering film with a thickness of 45 nm, and the shutter was closed once to interrupt the film formation. The shutter was opened again as the second layer, and the oxide was formed with a thickness of 45 nm through sputtering. The sputtering film was formed into a film, and a total film thickness of 90 nm was formed. The same procedure as in Example 1 was performed to obtain a transparent oxide laminated film of Example 19. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 20)
In Example 20, a sputtering target made of Sumitomo Metal Mine of Japan, which was blended so that the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.18, was used on a PEN thin film substrate made by Teijin. The first layer is formed with an oxide sputtered film having a thickness of 20 nm, and the shutter is closed to interrupt the film formation once. The shutter is opened again, and the second layer is sputtered to form an oxide with a thickness of 20 nm. The sputtering film was formed into a film, except that the total film thickness was 40 nm. The same procedure as in Example 1 was performed to obtain a transparent oxide laminated film of Example 20. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 21)
In Example 21, a sputtering target made by Sumitomo Metal Mine of Japan, which was blended so that the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.29, was used on a PEN film substrate made by Teijin. The first layer is formed with an oxide sputtered film having a thickness of 20 nm, and the shutter is closed to interrupt the film formation once. The shutter is opened again, and the second layer is sputtered to form an oxide with a thickness of 20 nm. The sputtering film was formed into a film, except that the total film thickness was 40 nm. The same procedure as in Example 1 was performed to obtain a transparent oxide laminated film of Example 21. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 22)
In Example 22, a transparent oxide laminated film of Example 22 was obtained in the same manner as in Example 6 except that a SiON film having a thickness of 100 nm was formed on a substrate made of Teijin's PEN film. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Example 23)
In Example 23, a transparent oxide laminated film of Example 23 was obtained in the same manner as in Example 6 except that a SiO ₂ film having a film thickness of 100 nm was formed on a PEN thin film substrate made by Teijin. . The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Comparative example 1)
Comparative Example 1 was performed in the same manner as in Example 1 except that a sputtering target manufactured by Sumitomo Metal Mine of Japan was used in which the atomic ratio Sn / (Zn + Sn) of Sn and Zn was adjusted to a ratio of 0.15, and was obtained. This is a transparent oxide laminated film of Comparative Example 1. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Comparative example 2)
Comparative Example 2 was performed in the same manner as in Example 1 except that the sputtering target made by Sumitomo Metal Mine of Japan was blended so that the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.30, and obtained. This is a transparent oxide laminated film of Comparative Example 2. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Comparative example 3)
In Comparative Example 3, a sputtering target made by Sumitomo Metal Mine of Japan, which was blended so that the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.17, was deposited on a PEN film substrate made by Teijin through sputtering. For the first layer, an oxide sputtered film having a thickness of 2.5 nm is formed by sputtering. The shutter is closed to interrupt the film formation once, and the shutter is opened again, and the film is sputtered as the second layer. An oxide sputtered film having a thickness of 2.5 nm was formed, and the oxide sputtered laminated film having a total film thickness of 5 nm was sputtered in the same manner as in Example 1 to obtain a transparent oxide laminated film of Comparative Example 3. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Comparative Example 4)
In Comparative Example 4, a sputtering target made by Sumitomo Metal Mine, Japan, which was blended so that the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.30, was applied on a PEN film substrate made by Teijin through sputtering. For the first layer, an oxide sputtered film having a thickness of 2.5 nm is formed by sputtering. The shutter is closed to interrupt the film formation once, and the shutter is opened again, and the film is sputtered as the second layer. An oxide sputtered film having a thickness of 2.5 nm was formed, and the oxide sputtered laminated film having a total film thickness of 5 nm was sputtered in the same manner as in Example 1 to obtain a transparent oxide laminated film of Comparative Example 4. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Comparative example 5)
In Comparative Example 5, a sputtering target made by Sumitomo Metal Mine of Japan, which was blended so that the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.18, was used on a PEN film substrate made by Teijin. A transparent oxide laminate film of Comparative Example 5 was obtained in the same manner as in Example 1 except that the oxide sputtering film was formed with a thickness of 100 nm. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Comparative Example 6)
In Comparative Example 6, a sputtering target made by Sumitomo Metal Mine, Japan, which was blended so that the atomic ratio Sn / (Zn + Sn) of Sn and Zn was 0.23, was used on a PEN thin film substrate made by Teijin. A transparent oxide laminated film of Comparative Example 6 was obtained in the same manner as in Example 1 except that the oxide was sputtered with a film thickness of 50 nm. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

(Comparative Example 7)
In Comparative Example 7, a sputtering target made by Sumitomo Metal Mine of Japan, which was prepared by mixing Sn and Zn with an atomic ratio Sn / (Zn + Sn) of 0.29, was used on a Teijin PEN film substrate. A transparent oxide laminate film of Comparative Example 7 was obtained in the same manner as in Example 1 except that the oxide was sputtered with a thickness of 10 nm. The crystallinity, water vapor transmission rate, and oxygen transmission rate were confirmed in the same manner as in Example 1.

The results of the above 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.

From Table 1, in all the examples in which Sn / (Zn + Sn) is in the range of 0.18 to 0.29, the water vapor transmission rate is 50 to 100 nm by the differential pressure method specified by the K7129 method according to JIS standards It is less than 0.0008 g / m ² / day, and in less than 50 nm, it is less than 0.004 g / m ² / day, and it is understood that it has excellent water vapor barrier performance. Furthermore, from Table 1, in all the examples in which Sn / (Zn + Sn) is in the range of 0.18 to 0.29, the oxygen transmission rate through the differential pressure method specified by the K7126 method in accordance with JIS standards is transparent. The total film thickness of the oxide laminated film is less than 0.008cc / m ² / day / atm when it is 50 ~ 100nm, and the total film thickness of the transparent oxide laminated film is less than 50nm, which is 0.04cc / Below m ² / day / atm, we know that those who have superior oxygen barrier performance. Therefore, in all the embodiments, the water vapor barrier performance and the good oxygen barrier performance become the above-mentioned ranges, and have the good water vapor barrier performance and the good oxygen barrier performance. In addition, the transmittance measured at a wavelength of 550 nm is also 90% or more and has transparency. In this way, the transparent oxide laminated film having the above-mentioned properties and having superior flexibility is obtained.

In addition, as in Examples 16 to 18, even if the number of atoms of Ta / (Zn + Sn + Ge + Ta) is 0.01, the ratio of the number of atoms of Ge to Ge / (Zn + Sn + Ge + Ta) is 0.04. The blended sputtering target showed good values for both water vapor transmission rate and oxygen transmission rate. However, the crystallinity was measured by X-ray diffraction, and it was amorphous in all of Examples 1 to 23.

On the other hand, in Comparative Examples 1 to 4, which are outside the range of Sn / (Zn + Sn) from 0.18 to 0.29, beyond the above numerical range, the water vapor barrier performance or oxygen barrier performance is inferior to the examples. . In addition, in Comparative Examples 5 to 7, which were only one-layer film formation, the above-mentioned numerical range was also exceeded, and the water vapor barrier performance or oxygen barrier performance was inferior to the examples.

From the above, according to the present invention, it is possible to provide a transparent oxide layered film with high mass productivity of direct current sputtering, excellent transparency, good water vapor barrier performance or oxygen barrier performance, and transparent oxide. Laminated film manufacturing method, sputtering target and transparent resin substrate.

However, as described above, the embodiments and embodiments of the present invention have been described in detail, but from the new matters and effects of the present invention, many modifications can be made without departing from the content. Can be easily understood. Accordingly, such modifications are included in the scope of the present invention.

For example, at least once in a specification or drawing, a term described at the same time as a different term that is broader or agreed may be replaced with a different term anywhere in the specification or drawing. In addition, the structures of the transparent oxide laminated film, the transparent oxide laminated film manufacturing method, the sputtering target and the transparent resin substrate are not limited to the structures described in the embodiments and examples of the present invention, but may be Implemented as various variants.

[Industrial possibilities]

The present invention uses oxidation with high water vapor barrier performance or oxygen barrier performance and high yield for direct bending. It has superior transparency, good water vapor barrier performance or oxygen barrier performance. Material sputtered laminated film, manufacturing method of oxide sputtered laminated film, transparent conductive film substrate (flexible display element, etc.) of oxide sintered body and transparent resin substrate are used as OLED display element, QD display element, QD plate, etc. Components are extremely useful.

Claims (10)

A transparent oxide laminated film 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 is characterized in that: An amorphous film having a metal atomic ratio of Zn to Sn of two or more layers having an Sn / (Zn + Sn) of 0.18 or more and 0.29 or less. The transparent oxide laminate film according to item 1 of the scope of application, wherein the thickness of the transparent oxide laminate film is 100 nm or less. For example, the transparent oxide laminated film described in the first patent application range, wherein at least one of the transparent oxide films contains Ta and Ge, The Ta / (Zn + Sn + Ge + Ta) of the metal atomic ratio of the aforementioned Ta to Zn, Sn, and Ge is 0.01 or less, Ge / (Zn + Sn + Ge + Ta) of the metal atomic ratio of Ge to Zn, Sn, and Ta is 0.04 or less. For example, the transparent oxide laminated film described in the first patent application scope, wherein the water vapor transmission rate through the differential pressure method specified by the JIS standard K7129 method is the total film thickness of the transparent oxide laminated film. When it is 50 to 100 nm, it is 0.0008 g / m ² / day or less, and when the total film thickness of the transparent oxide laminate film is less than 50 nm, it is 0.004 g / m ² / day or less. For example, if the transparent oxide laminated film described in item 1 of the patent application scope has an oxygen transmission rate through a differential pressure method specified by the JIS standard K7126 method, the total film thickness of the transparent oxide laminated film is 50 ~ 100nm as 0.008cc / m ² / day / atm or less, and the total thickness of the laminated film of the transparent oxide layer is less than 50nm, in order to 0.04cc / m ² / day / atm or less persons. A sputtering target is a sputtering target used for forming a transparent oxide layered film as described in any one of claims 1 to 5 of a patent application scope by a sputtering method, and is characterized in that: It is constructed by a Sn-Zn-O-based oxide sintered body, a bonding material, and a back plate. The Sn / (Zn + Sn) ratio of the metal atomic ratio of Zn to Sn contained in the oxide sintered body is 0.18 or more and 0.29 or less. For example, the sputtering target described in item 6 of the patent application scope is characterized in that the aforementioned oxide sintering system further contains Ta and Ge, The Ta / (Zn + Sn + Ge + Ta) of the metal atomic ratio of the aforementioned Ta to Zn, Sn, and Ge is 0.01 or less, Ge / (Zn + Sn + Ge + Ta) of the metal atomic ratio of Ge to Zn, Sn, and Ta is 0.04 or less. A method for manufacturing a transparent oxide layered film is a method for manufacturing a transparent oxide layered film that is sputtered using a target made of a Sn-Zn-O system oxide sintered body, which is characterized in that: The target is an oxide sintered body having a metal atomic ratio and a Sn / (Zn + Sn) of 0.18 or more and 0.29 or less, When the sputtering is interrupted at least once during the film formation, a transparent oxide laminate film having two or more amorphous films is formed. For example, the method for manufacturing a transparent oxide laminated film according to item 8 of the scope of application for a patent, wherein the film thickness of the transparent oxide laminated film is 100 nm or less. A transparent resin substrate, characterized in that the transparent oxide laminate film described in any one of claims 1 to 5 of the patent application scope is formed on at least one surface of a transparent resin substrate.