TW201936953A - Oxide sputtered film, method for manufacturing oxide sputtered film, oxide sintered compact, and transparent resin substrate - Google Patents

Abstract

The purpose of the present invention is to provide an oxide sputtered film having excellent transparency and good water vapor barrier performance and oxygen barrier performance in high-mass-productivity direct-current sputtering, a method for manufacturing an oxide sputtered film, an oxide sintered compact, and a transparent resin substrate. An oxide sputtered film which contains Zn and Sn, is amorphous and transparent, and has water vapor barrier performance or oxygen barrier performance, the oxide sputtered film being characterized in that the ratio Sn/(Zn + Sn) of the number of metal atoms of Zn and Sn therein is 0.18 to 0.29.

Description

Oxide sputter film, method for producing oxide sputter film, oxide sintered body, and transparent resin substrate

The present invention relates to an amorphous transparent oxide sputtering film containing Zn and Sn, a method for producing the same, an oxide sintered body for forming an oxide sputtering film, and a transparent resin which is formed on a substrate by a film-forming oxide sputtering film. Substrate. The present application claims priority on the basis of Japanese Patent Application No. 2018-015770, filed on Jan. 31, 2011, the entire disclosure of which is hereby incorporated by reference.

A resin substrate coated with a metal oxide film having a water vapor barrier property and an oxygen barrier property as a barrier film of ruthenium oxide or aluminum oxide on the surface of a transparent resin substrate such as a plastic substrate or a film substrate is used to prevent It is used for packaging purposes such as intrusion of water vapor and oxygen, and prevention of deterioration of foods or medicines. In recent years, it has also been used in liquid crystal display elements, solar cells, electroluminescence display elements (EL elements), quantum dot (QD) display elements, quantum dot sheets (QD sheets), and the like.

In the past few years, in addition to the need for weight reduction and enlargement, it is required for the degree of freedom of shape, in addition to the need for weight reduction and enlargement, in the electronic device, in particular, the transparent resin substrate having the water vapor barrier property or the oxygen barrier property used for the display device. Surface display and other requirements such as flexibility. The correspondence between the glass substrates used so far has been strict, and the use of a transparent resin substrate has begun.

However, since the base material of the transparent resin substrate is inferior in water vapor barrier properties or oxygen barrier properties to the substrate of the glass substrate, water vapor and oxygen permeate through the substrate to deteriorate the EL display element, the QD display element, and the like. The problem. In order to improve such problems, development of a transparent resin substrate in which a metal oxide film is formed on a substrate of a flexible substrate to improve water vapor barrier properties or oxygen barrier properties has been carried out.

In particular, when an EL display device or a QD display device is used in practical use, when such a display such as an organic EL display is used, it is known that if an organic EL display element is mixed with water vapor or oxygen, the interface between the cathode layer and the organic layer is affected by moisture. Or the damage caused by oxidation is greatly affected, and there is a problem that the organic layer and the cathode portion are peeled off or a dark spot of the unexposed portion is generated, and the performance is remarkably lowered. It can be said that the water vapor transmission rate (WVTR) required for the transparent resin substrate usable in these displays is 0.01 g/m ² /day or less, preferably 0.005 g/m ² /day or less, and the oxygen transmission rate (OTR). It was 0.1cc / m ² / day / atm less, and preferably 0.05cc / m ² / day / atm less. Further, these displays have requirements for flexibility and the like, and the expectation of thinning of a transparent resin substrate having a water vapor barrier property or an oxygen barrier property is also greatly improved. For example, the film 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. Accordingly, it is described that the water vapor transmission rate at 40 ° C and 90% RH is 5 × 10 ^-4 g / (m ² · day) or less. The film thickness is 25 nm or more and 100 nm or less.

Further, in Patent Document 2, it is proposed to have an organic film layer and a gas barrier layer, and a barrier film of a gas barrier layer is formed 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.

Further, Patent Document 3 describes a gas barrier transparent resin substrate (film) in which a tin oxide-based transparent conductive film is formed by sputtering on a transparent resin substrate (film). Although the water vapor transmission rate was less than 0.01 g/m ² /day, the transparent resin substrate (film) used was 200 μm, and the thickness of the barrier film was 100 to 200 nm.

Further, Patent Document 4 describes a method in which a tantalum nitride film is formed on a resin film substrate by a sputtering method.

Further, in Patent Document 5, it is proposed to use a laminated mixed film of fluorine, oxonium, aluminum oxide film or the like. At this time, the oxygen permeability 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 barrier layer thickness at this time is 200 to 1000 angstroms.
[Previous Technical Literature]
[Patent Literature]

[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 Patent Laid-Open Publication No. 2002-100469
[Patent Document 5] Japanese Patent No. 2892793

[Questions to be solved by the invention]

However, in the film formation method of Patent Document 1, although the film thickness is small and the water vapor transmission rate is 0.005 g/m ² /day or less, the atomic layer deposition film method of the film formation method is particularly required, and an expensive device must be purchased. Moreover, it is not possible to use it in mass production because of the slow film formation rate and poor productivity. In the plasma CVD method of the film formation method of Patent Document 2, although the film formation rate is high, the film thickness or characteristics of the formed gas barrier film are likely to vary and the stability is low. The film is also poor in breadth and has a film thickness of 0.2 to 2 μm and is relatively thick, so that the film has poor flexibility.

Further, Patent Document 3, which uses a sputtering method widely used in the industry, measures the water vapor transmission rate by the Mocon method, but it is difficult to accurately measure to 0.01 g/m ² /day by the measurement of the moire method. Below, there is still doubt about the actual membrane water vapor barrier properties. Further, the film thickness is 100 to 200 nm and is thick, so the flexibility is poor. In Patent Document 4, the tantalum nitride film has better gas barrier properties than the tantalum oxide film or the aluminum oxide film. However, since it is generally a colored film, the gas barrier of the transparent resin substrate for display which is necessary for transparency cannot be used. membrane. Further, even if a part of the nitrogen of the tantalum nitride is replaced by oxygen and becomes non-colored, the film thickness is 200 nm, which is thick and inferior in flexibility. Patent Document 5 describes a film which has both an oxygen transmission rate and a water vapor transmission rate by using a plurality of films such as aluminum oxide, but there is no sufficient characteristic in the current state.

As a barrier film used for an EL display element, a QD display element, or the like, a film formed by a sputtering method widely used in the industry is used, and it is required to have a film thickness and a good water vapor transmission rate and oxygen permeability. High characteristics.

Accordingly, the present invention has been made in view of such requirements, and an object thereof is to provide an oxide sputtering film or oxide having excellent transparency, good water vapor barrier properties, or oxygen barrier properties by using high-volume DC sputtering. A method for producing a sputtering film, an oxide sintered body, and a transparent resin substrate.

[Means to solve the problem]

An aspect of the present invention is an oxide sputtering film characterized by an amorphous oxide transparent film of Zn and Sn having a water vapor barrier property or an oxygen barrier property, and the metal atomic ratio of the Zn and Sn The Sn/(Zn+Sn) is 0.18 or more and 0.29 or less.

According to this, it is possible to provide an oxide sputter film which is excellent in transparency, good water vapor barrier properties or oxygen barrier properties by utilizing high-volume DC sputtering.

In this case, in one aspect of the invention, the oxide sputtering film has a film thickness of 100 nm or less.

According to this, it is possible to provide an oxide sputter film having a water vapor barrier property or an oxygen barrier property of 100 nm or less and which is more excellent in flexibility.

In one aspect of the invention, the oxide sputtering film further contains Ta and Ge, and the ratio of the number of metal atoms of Ta to Zn, Sn, and Ge is less than or equal to 0.01 (Ta+(Zn+Sn+Ge+Ta)). The ratio of the number of metal atoms of Ge to Zn, Sn, and Ta is Ge/(Zn+Sn+Ge+Ta) of 0.04 or less.

According to this, the film formation speed can be improved by improving the conductivity of the target itself, and the density of the target can be increased to form a film stably, thereby providing an oxide sputtering film having excellent water vapor barrier properties or oxygen barrier properties.

In this case, in one aspect of the present invention, the water vapor transmission rate measured by the differential pressure method specified by the K7129 method of JIS standard is 0.005 g/ when the film thickness of the oxide sputtering film is 50 to 100 nm. m ² /day or less, when the film thickness of the oxide sputtering film is less than 50 nm, it is 0.009 g/m ² /day or less, and further, in one aspect of the present invention, the differential pressure specified by the K7126 method according to JIS standard The oxygen permeability measured by the method is 0.05 cc/m ² /day/atm or less when the film thickness of the oxide sputtering film is 50 to 100 nm, and when the film thickness of the oxide sputtering film is less than 50 nm, 0.09 cc / m ² /day / atm or less.

Accordingly, it is possible to provide an oxide sputter film in a flexible OLED display element or a QD display element which is one of the flexible display elements and which has good water vapor barrier properties or oxygen barrier properties.

An aspect of the present invention is an oxide sintered body characterized by a Sn-Zn-O-based oxide sintered body for forming an oxide sputtering film by sputtering, wherein the oxide sintered body contains The ratio of the number of metal atoms of Zn to Sn is Sn/(Zn+Sn) of 0.18 or more and 0.29 or less.

According to this, it is possible to provide an oxide sintered body for use in an oxide sputtering film which is excellent in transparency, good water vapor barrier property or oxygen barrier property by sputtering using a high-volume DC sputtering. .

In one aspect of the invention, the oxide sintered body further contains Ta and Ge, and the ratio of the metal atomic ratio of Ta to Zn, Sn, and Ge is Ta/(Zn+Sn+Ge+Ta). Hereinafter, the Ge/(Zn+Sn+Ge+Ta) ratio of the metal atomic ratio of Ge to Zn, Sn, and Ta may be 0.04 or less.

According to this, the film formation speed can be improved by improving the conductivity of the sintered body, and the sintered density of the sintered body can be increased to form a film stably, and an oxide sputtering film having excellent water vapor barrier properties or oxygen barrier properties can be provided.

One aspect of the present invention is a method for producing an oxide sputter film characterized by sputtering using a target made of an oxide sintered body of a Sn-Zn-O system to obtain an amorphous material containing Zn and Sn. In the film which is transparent and has a water vapor barrier property or an oxygen barrier property, the Sn/(Zn+Sn) ratio of the metal atomic ratio of Zn to Sn contained in the oxide sintered body used for the sputtering is 0.18 or more and 0.29 or less.

According to this, it is possible to provide a method for producing an oxide sputter film which has excellent transparency, good water vapor barrier properties or oxygen barrier properties by using DC sputtering with high mass productivity.

In this case, in one aspect of the invention, the oxide sputtering film may have a film thickness of 100 nm or less.

According to this, it is possible to provide a method for producing an oxide sputter film having a water vapor barrier property or an oxygen barrier property of 100 nm or less and which is more excellent in flexibility.

One aspect of the present invention is a transparent resin substrate characterized in that a transparent substrate is formed on a transparent substrate to form an amorphous oxide transparent film having Zn and Sn and having an oxide sputtering property or an oxygen barrier property. In the resin substrate, the oxide sputtering film is formed on at least one surface of the substrate, and the ratio of the number of metal atoms of Zn to Sn is Sn/(Zn+Sn) of 0.18 or more and 0.29 or less, and the film thickness of the oxide sputtering film is It is 100 nm or less.

According to this, it is possible to provide a transparent resin substrate having an oxide sputter film having excellent transparency, good water vapor barrier properties, or oxygen barrier properties on a transparent substrate by using DC sputtering with high mass productivity.

[Effect of the invention]

According to the present invention, an oxide sputtering film having excellent transparency, good water vapor barrier properties or oxygen barrier properties, a method for producing an oxide sputtering film, an oxide sintered body, and the like can be provided. Transparent resin substrate.

The present invention described below is not intended to limit the scope of the invention as described in the appended claims. Further, the configurations described in the present embodiment are not necessarily limited to the means for solving the invention. An oxide sputtering film, a method for producing an oxide sputtering film, an oxide sintered body, and a transparent resin substrate according to an embodiment of the present invention will be described in the following order.
Oxide sputter film
2. Oxide sintered body
3. Method for manufacturing oxide sputter film
4. Transparent resin substrate

<1. Oxide Sputtering Film>
The oxide sputter 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. The surface of the flexible display element such as a plastic substrate or a film substrate such as a liquid crystal display element, a solar cell, or an electroluminescence (EL) display element is covered as a metal oxide film by sputtering, based on being blocked by water It is used for the purpose of preventing deterioration by steam or oxygen.

The oxide sputter film 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 the defects (gap) through which moisture or oxygen passes are small. Therefore, the oxide barrier film is formed by a sputtering method to be described later. The oxide sputter film formed by the sputtering method is preferably amorphous as in Patent Document 3.

When the oxide sputtering film is a crystalline film, the crystal grain boundary exists in the film, and water vapor or oxygen permeates through the crystal grain boundary, so that the water vapor barrier performance or the oxygen barrier property is lowered. Further, in Patent Document 3, a tin oxide film as the amorphous film is proposed, but when a tin oxide film is formed by a sputtering method, a target for a sputtering target used for sputtering is used. The tin oxide system of the same composition. The tin oxide-based target generally has high acid resistance but a low relative density of the target, and there are many problems in that sputtering cannot be stably formed due to cracking of the target, etc., but Sn-Zn-described later is used. The O-series sputtering target finally dispels the concerns.

That is, the oxide sputter film according to an embodiment of the present invention is characterized by an oxide sputter film having amorphous and transparent Zn and Sn and having water vapor barrier properties or oxygen barrier properties, and the metal atomic ratio of the above Zn and Sn The Sn/(Zn+Sn) is 0.18 or more and 0.29 or less.

As described above, by using Sn/(Zn + Sn) in a ratio of metal atomic number of 0.18 or more and 0.29 or less, good water vapor barrier properties or oxygen barrier properties can be obtained.

When the number of metal atoms is less than 0.18, the ratio of SnO ₂ is small, so that precipitation of ZnO having high crystallinity is increased, and a part of crystallized portion (microcrystalline state) increases in the film. The inflow of water vapor or oxygen from the crystal grain boundary becomes large, and an oxide sputter film having desired water vapor barrier properties or oxygen barrier properties cannot be obtained.

On the other hand, when the ratio of the number of metal atoms Sn/(Zn+Sn) is more than 0.29, since the ratio of SnO ₂ is increased, the stress of the film is increased, and the heat generation during film formation is increased, and film peeling or the like occurs. In the damage of the substrate, an oxide sputter film having water vapor barrier properties or oxygen barrier properties which can be used in OLED, QD or the like cannot be obtained.

Preferably, the oxide sputter film further contains Ta and Ge, and the ratio of the number of metal atoms of Ta to Zn, Sn, and Ge is 0.01/s or less of Ta/(Zn+Sn+Ge+Ta), and the Ge and Zn, Sn, and Ta are The ratio of the number of metal atoms to Ge/(Zn+Sn+Ge+Ta) is 0.04 or less.

Even if Ta or Ge is contained, since the crystallization temperature is 600 ° C or more, an amorphous film structure is easily obtained. Further, since the crystallization temperature is high, it is possible to easily maintain the amorphous state even when there is heat influence in the mass production step process. Further, by adding Ta or Ge at the above ratio, the effect of the characteristics of the sputtering target containing Zn and Sn is further enhanced. The details will be described later.

Moreover, there is no influence on the oxide sputter film which is formed by sputtering the target to which Ta and Ge are added. For example, the effects of water vapor transmission rate, oxygen permeability, and the like are not confirmed. Therefore, Sn/(Zn+Sn) is 0.18 or more and 0.29 or less, and Ta/(Zn+Sn+Ge +Ta) is 0.01 or less in Ge atomic ratio, and Ge/(Zn+Sn+Ge+Ta) It is contained in a ratio of 0.04 or less, and the water vapor barrier property or the oxygen barrier property is not deteriorated, and an amorphous oxide sputtering film having good characteristics can be obtained.

The film thickness of the above oxide sputtering film is preferably 100 nm or less. According to this, it is possible to provide an oxide sputter film having a water vapor barrier property or an oxygen barrier property of 100 nm or less and which is more excellent in flexibility. Further, it is preferably 90 nm or less.

Further, the water vapor transmission rate measured by the differential pressure method specified by the K7129 method of JIS standard is preferably 0.005 g/m ² /day or less when the film thickness of the oxide sputtering film is 50 to 100 nm. When the film thickness of the above oxide sputtering film is less than 50 nm, it is 0.009 g/m ² /day or less.

In addition, when the water vapor transmission rate measured by the differential pressure method specified by the K7129 method of the JIS standard is 0.01 g/m ² /day or more, the OLED display element or the QD display element is mixed with water vapor and internally. The interface of the display element layer or the like is rapidly deteriorated by moisture, and early peeling occurs, which is difficult to use as a device for a long period of time. More preferably, it is 0.005 g/m ² /day or less.

The oxygen permeability measured by the differential pressure method specified by the K7126 method of JIS standard is preferably 0.05 cc/m ² /day/atm or less at the film thickness of the oxide sputtering film of 50 to 100 nm. When the film thickness of the sputtering film is less than 50 nm, it is preferably 0.09 cc/m ² /day/atm or less.

In addition, when the oxygen permeability measured by the differential pressure method specified by the K7126 method of the JIS standard is 0.1 cc/m ² /day/atm or more, the OLED display element or the QD display element is mixed with oxygen due to internal combustion. The interface of the display element layer or the like is deteriorated due to oxygen, and early peeling occurs, which is difficult to use as a device for a long period of time. More preferably, it is 0.05 cc/m ² /day/atm or less.

When the thickness of the oxide-sputtered film is less than 10 nm, the oxide-sputtered film is too thin, and it is difficult to ensure the film thickness of the entire film of the transparent resin substrate to be described later, and it is easy to pass water vapor or oxygen due to a slight defect. When the thickness of the oxide sputter film is thick, it is likely to cause damage to the film due to stress or the like, and the possibility of water vapor permeation is high. Further, when the thickness of the oxide sputter film is thick, the flexibility is deteriorated. In view of productivity and cost, the film thickness is preferably 100 nm or less. Therefore, it is used at 10 to 100 nm, which is suitable for flexibility, light weight, or thin film formation, and is the most suitable film thickness for use in assembly or mass production.

As described above, the oxide sputter film according to an embodiment of the present invention can have excellent transparency, good water vapor barrier properties, or oxygen barrier properties.

<2. Oxide sintered body>
Next, an Sn-Zn-O-based oxide sintered body for forming the above-described oxide sputtering film by sputtering will be described. An oxide sintering system according to an embodiment of the present invention is a Sn-Zn-O-based oxide sintered body comprising a sputtering target used for sputtering an oxide sputtering film.

In addition, the Sn/(Zn+Sn) ratio of the metal atomic ratio of Zn and Sn contained in the oxide sintered body is 0.18 or more and 0.29 or less. The characteristics of the above oxide sintered body are continued to the oxide sputtering film.

Therefore, when the ratio of the number of metal atoms of Zn and Sn contained in the oxide sintered body is less than 0.18, the ratio of SnO ₂ is small, so that the precipitation of ZnO having high crystallinity is increased. The portion of the inner crystallized portion (microcrystalline state) is increased, so that the inflow of water vapor or oxygen from the crystal grain boundary is increased, and an oxide sputter film having desired water vapor barrier properties or oxygen barrier properties cannot be obtained.

On the other hand, when the ratio of the number of metal atoms is greater than 0.29, the ratio of SnO ₂ is increased, so that the stress of the film becomes strong, and the heat generation during film formation becomes large, and film peeling or base formation occurs. In the damage of the material, an oxide sputter film having water vapor barrier properties or oxygen barrier properties which can be used in OLED, QD or the like cannot be obtained.

Further, the oxide sintered body composed only of the composition of Sn-Zn has insufficient conductivity and a large specific resistance value. In the case of sputtering, when the specific resistance value is larger, sputtering must be performed with a larger energy, and the film formation speed cannot be increased. Therefore, it is necessary to reduce the electrical conductivity of the sintered body used for the target. In the oxide sintered body, since Zn ₂ SnO ₄ , ZnO, and SnO ₂ are incapable of being electrically conductive, even if the compounding ratio is adjusted and the amount of the compound phase or ZnO or SnO _{2 is} adjusted, the conductivity cannot be greatly improved.

Therefore, it is preferred to add Ta in a specific amount. Since ZnO and Zn Ta will be the phase, Zn Sn displacement of phase ₂ SnO Zn ₄ or Sn, SnO ₂ and phase of a solid solution, without forming a crystalline structure of the ZnO wurtzite phase, spinel A compound phase other than the Zn ₂ SnO ₄ phase of the crystal structure and the SnO ₂ phase of the rutile crystal structure. By adding Ta, the density of the oxide sintered body can be maintained and the conductivity can be improved.

Further, the sintered sintered body having only a composition of Sn-Zn has a sintered density of about 90%, which is not sufficient. When the density of the oxide sintered body is low, there is a problem that it is impossible to form a film stably due to cracking of the oxide sintered body or the like during sputtering.

Therefore, it is preferred to add Ge in a specific amount. Since Ge in the oxide sintered body, and will phase of Zn ZnO, Zn ₂ SnO Zn ₄ phase or the Sn Sn, SnO ₂ phase of the substitution solution, without forming a wurtzite type crystal structure of a ZnO phase, a spinel crystal structure of a Zn ₂ SnO ₄ phase, and a rutile crystal structure of a SnO ₂ phase other than a compound phase. By adding Ge, it has an effect of densifying the oxide sintered body. Thereby, the sintered density of the oxide sintered body can be made higher.

Therefore, the oxide sintered body preferably further contains Ta and Ge, and the Ta/(Zn+Sn+Ge+Ta) ratio of the metal atomic ratio of Ta to Zn, Sn, and Ge is 0.01 or less, and the Ge and Zn, Sn, and The metal atomic ratio of Ta is Ge/(Zn+Sn+Ge+Ta) of 0.04 or less.

Further, when Ta/(Zn+Sn+Ge+Ta) ratio of the metal atomic ratio of Ta to Zn, Sn, and Ge is more than 0.01, a compound phase such as Ta ₂ O ₅ or ZnTa ₂ O _{6 is} formed. Therefore, the conductivity cannot be greatly improved.

Further, when Ge/(Zn+Sn+Ge+Ta) of the ratio of the number of metal atoms of Ge to Zn, Sn, and Ta is more than 0.04, oxidation occurs due to formation of a compound phase such as Zn ₂ Ge ₃ O ₈ or the like. The density of the sintered body of the material becomes low, and the target becomes susceptible to cracking during sputtering.

The method for producing the sintered body is specifically exemplified below, but is not limited thereto. First, an oxide powder of Zn, an oxide powder of Sn, and an oxide powder containing an additive element of Ta and Ge are adjusted to a preferred metal atomic ratio described above and mixed. Next, the granulated powder is added to pure water or ultrapure water, an organic binder, a dispersant, an antifoaming agent, and mixed.

Next, the raw material powder is wet-pulverized using a bead polishing apparatus or the like into which a hard ZrO ₂ ball is introduced, and then mixed and stirred to obtain a slurry. The obtained slurry is sprayed and dried in a spray dryer apparatus or the like to obtain a granulated powder.

Next, the granulated powder is subjected to press molding to obtain a molded body. In order to remove the inter-particle pores of the granulated powder, press forming is performed at a pressure of, for example, about 294 MPa (3.0 ton/cm ² ). The method of press molding is not particularly limited, but it is preferred to fill the granulated powder in a rubber mold, for example, using cold isostatic pressing (CIP: Cold Isostatic Press) which can apply a high pressure.

Next, the formed body is fired to obtain an oxide sintered body. In the specific temperature increase rate in the firing furnace, the formed body is fired at a specific temperature and for a specific time to obtain an oxide sintered body. The firing is performed, for example, in an atmosphere of a firing furnace in the atmosphere. It is preferred to fire the molded body at a rate of temperature increase from 700 ° C to a specific sintering temperature in the sintering furnace of 0.3 to 1.0 ° C / min. This is because it promotes the diffusion of ZnO, SnO ₂ or Zn ₂ SnO ₄ compounds, improves the sinterability, and improves the conductivity. Further, by setting this temperature increase rate, it also has an effect of suppressing volatilization of ZnO or Zn ₂ SnO ₄ in a high temperature region.

When the temperature increase rate in the sintering furnace is less than 0.3 ° C / min, the diffusion of the compound is lowered. On the other hand, when it exceeds 1.0 ° C / min, since the temperature increase rate is rapid, 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 from 1300 ° C to 1400 ° C. When the sintering temperature is less than 1300 ° C, the temperature is too low, and grain boundary diffusion of sintering of ZnO, SnO ₂ or Zn ₂ SnO ₄ compound is not performed. On the other hand, when the temperature exceeds 1400 ° C, the grain boundary diffusion is promoted to progress the sintering, but the volatilization of the Zn component cannot be suppressed, and large pores are left inside the oxide sintered body.

The holding time after the temperature rise is preferably from 15 hours to 25 hours. When the holding time was less than 15 hours, since the sintering was incomplete, the sintered body having a large deformation or warpage was formed, and the grain boundary diffusion did not proceed, and the sintering did not progress. As a result, a dense sintered body cannot be produced. On the other hand, when it exceeds 25 hours, volatilization of ZnO or Zn ₂ SnO ₄ increases, and the density of an oxide sintered compact falls, work efficiency deteriorates, and cost is high.

As described above, according to the oxide sintered body according to the embodiment of the present invention, an oxide sputtering film having excellent transparency, good water vapor barrier properties, or oxygen barrier properties can be obtained by DC sputtering with high mass productivity.

Further, a sputtering target composed of an oxide sintered body was produced by the following. First, the oxide sintered body is subjected to mechanical grinding to obtain a desired size, and a processed body (target) is obtained. The obtained processed body is bonded (bonded) to a backing plate made of a copper material, a stainless steel material or the like using a bonding material such as indium (In) or the like to obtain a sputtering target. The sputtering target may be formed by laminating a plurality of oxide sintered bodies.

<3. Method for Producing Oxide Sputtered Film>
Next, a method of producing an oxide sputter film according to an embodiment of the present invention will be described. In the method for producing an oxide sputter film according to an embodiment of the present invention, sputtering is performed using a target made of an Sn-Zn-O-based oxide sintered body to obtain amorphous and transparent Zn and Sn-containing water vapor. A barrier to barrier performance or oxygen barrier properties.

In addition, Sn/(Zn+Sn) having a ratio of the number of metal atoms of Zn and Sn contained in the oxide sintered body used for the sputtering is 0.18 or more and 0.29 or less. Further, the technical significance of the above range is as described above.

Further, it is characterized in that the film thickness of the oxide sputtering film is 100 nm or less. As described above, according to this, it is possible to provide an oxide sputter film having a water vapor barrier property or an oxygen barrier property of 100 nm or less and which is more excellent in flexibility.

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

As the sputtering condition, the degree of vacuum in the chamber was adjusted to 1 × 10 ^-4 Pa or less. The environment inside the chamber is introduced with an inert gas. The inert gas is argon gas or the like, and the purity is preferably 99.999 mass% or more. Further, the inert gas contains 4 to 10% by volume of oxygen with respect to the entire gas flow rate. Since the oxygen concentration affects the surface resistance value of the film, the oxygen concentration is set so as to be a specific resistance value. Subsequently, a specific DC power source is used to supply a power source between the sputtering target and the substrate, and a plasma is generated by a DC pulse to form a film by sputtering. Further, the film thickness is controlled by the film formation time.

The water vapor barrier properties or oxygen barrier properties of the oxide sputtered film can be obtained in a manner that is less dependent on the sputtering conditions. Even when the conditions are adjusted according to the state of the required transmittance and the resistance value, it is possible to easily form a film having good water vapor barrier properties or oxygen barrier properties.

As described above, according to the method for producing an oxide sputter film according to an embodiment of the present invention, an oxide sputter film having excellent transparency, good water vapor barrier properties, or oxygen barrier properties 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 formed by forming an oxide sputter film containing amorphous and transparent Zn and Sn and having water vapor barrier properties or oxygen barrier properties on a transparent substrate. Further, the oxide sputtering film is formed on at least one surface of the substrate, and the ratio of the number of metal atoms of Zn to Sn is Sn/(Zn+Sn) of 0.18 or more and 0.29 or less. Further, the film thickness of the oxide sputtering film described above is 100 nm or less.

As the transparent substrate, polyethylene terephthalate, polyethylene, naphthalate, polycarbonate, polyfluorene, polyether oxime, polyarylate, cycloolefin polymer, fluororesin, poly Propylene, polyimine resin, epoxy resin, and the like. Further, the thickness of the transparent resin substrate is not particularly limited, but it is preferably from 50 to 150 μm in view of flexibility, cost, or equipment requirements.

The sputtering of the transparent resin substrate may be performed by sputtering as described in the method for producing an oxide sputter film. Further, the technical significance of the preferred metal atomic ratio or film thickness of Zn and Sn is as described above.

Further, in the transparent resin substrate according to the embodiment of the present invention, an oxide sputter film containing amorphous and transparent Zn and Sn and having water vapor barrier properties or oxygen barrier properties is formed on at least one surface of the transparent substrate. It can also be laminated by interposing other films. For example, a ruthenium oxide film or a ruthenium nitride film, a resin film, a wet coating film, a metal film, an oxide film, or the like is formed on the substrate, and then the oxide sputtering film may be formed as water vapor on at least one of the substrates. Barrier layer or oxygen barrier layer.

According to the transparent resin substrate of one embodiment of the present invention, a flexible OLED display element, a flexible QD display element, or a QD sheet, for example, one of the flexible display elements can be formed.

As described above, the transparent resin substrate according to the embodiment of the present invention can have excellent transparency, good water vapor barrier properties, or oxygen barrier properties by utilizing DC sputtering with high mass productivity.

[Examples]

Next, an oxide sputter film, a method for producing an oxide sputter film, an oxide sintered body, and a transparent resin substrate according to an embodiment of the present invention will be described in detail by way of examples. Further, the invention is not limited to the embodiments.

(Example 1)
In Example 1, SnO ₂ powder, ZnO powder, Ta ₂ O ₅ powder as an additive element Ta, and GeO ₂ powder as an additive element Ge were separately prepared.

A sintered body produced by using zinc oxide as a main component and tin oxide having a metal atomic ratio of Sn/(Zn+Sn) of 0.23 is used as a sputtering target (manufactured by Sumitomo Metal Mine), and a sputtering apparatus is used for the sputtering target. Sputtered into a film. This sputtering apparatus used a DC magnetron sputtering apparatus (manufactured by ULVAC, Model SH-550).

Film formation of the amorphous oxide sputtering film was carried out under the following conditions. A target is mounted on the cathode, and a resin film substrate is 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 formation is performed is stationary on the opposite surface of the cathode, and the film formation is performed in a stationary direction. As the resin film substrate, a PEN film (manufactured by Teijin, thickness: 50 μm) was used. When the degree of vacuum in the chamber reaches 2×10 ⁻⁴ Pa or less, argon gas having a purity of 99.9999% by mass is introduced into the chamber to set the gas pressure to 0.6 Pa, and a DC power source device is used in argon gas containing 5 vol% of oxygen. (DMX company, MDX) As a DC power supply, a DC power of 1500W using a DC pulse of 20 kHz was applied between the sputtering target and the PEN film substrate. The plasma was generated by DC pulse and sputtered by Teijin. An oxide sputter film having a film thickness of 100 nm was formed on the PEN film substrate.

The crystallinity, water vapor transmission rate (WVTR), and oxygen transmission rate (OTR) of the oxide sputtering film prepared as described above were confirmed. The crystallinity was measured by X-ray diffraction measurement and diffraction peak, and the water vapor transmission rate was measured by a differential pressure method (DELTAPERM-UH manufactured by Technolox Co., Ltd.). The oxygen permeability was also measured by a differential pressure method (GTR-2000X manufactured by GTR Techno Co., Ltd.). Further, the transmittance was measured by a spectrophotometer using the average visible light transmittance at a wavelength of 550 nm.

(Example 2)
In Example 2, the oxide of Example 2 was obtained in the same manner as in Example 1 except that the Sputtered Metal Mine Sputtering Target prepared by using the ratio of the atomic ratio of Sn to Zn to Sn/(Zn+Sn) of 0.18 was used. Sputtered film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, and the oxygen permeability were confirmed.

(Example 3)
In Example 3, the oxide splash of Example 3 was obtained in the same manner as in Example 1 except that the Sumitomo Metal Mine sputtering target prepared by using the ratio of the atomic ratio of Sn to Zn to Sn/(Zn+Sn) of 0.28 was used. Coating. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Example 4)
In Example 4, an oxide having a thickness of 10 nm was obtained on a PEN film substrate manufactured by Teijin PEI film substrate except that a Sumitomo Metal Mine sputtering target prepared by using an atomic ratio of Sn to Zn of Sn/(Zn+Sn) of 0.23 was used. An oxide sputter film of Example 4 was obtained in the same manner as in Example 1 except for the sputtering film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Example 5)
In Example 5, an oxide having a film thickness of 50 nm was obtained on a PEN film substrate manufactured by Teijin PEI film substrate, except that a Sumitomo Metal Mine sputtering target prepared by using an atomic ratio of Sn to Zn of Sn/(Zn+Sn) of 0.23 was used. An oxide sputter film of Example 5 was obtained in the same manner as in Example 1 except for the sputtering film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Example 6)
In Example 6, except for the Sumitomo Metal Mine Sputtering Target prepared by using the ratio of the atomic ratio of Sn to Zn to Sn/(Zn+Sn) of 0.18, an oxide having a film thickness of 10 nm was obtained on a PEN film substrate manufactured by Teijin. An oxide sputter film of Example 6 was obtained in the same manner as in Example 1 except for the sputtering film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Example 7)
In Example 7, except for the Sumitomo Metal Mine Sputtering Target prepared by using the ratio of the atomic ratio of Sn to Zn to Sn/(Zn+Sn) of 0.18, an oxide having a film thickness of 50 nm was obtained on a PEN film substrate manufactured by Teijin. An oxide sputter film of Example 7 was obtained in the same manner as in Example 1 except for the sputtering film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Example 8)
In Example 8, an oxide of 10 nm in thickness was obtained on a PEN film substrate manufactured by Teijin PEI film substrate except that a Sumitomo Metal Mine sputtering target prepared by using an atomic ratio of Sn to Zn of Sn/(Zn+Sn) of 0.28 was used. An oxide sputter film of Example 8 was obtained in the same manner as in Example 1 except for the sputtering film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Example 9)
In Example 9, an oxide having a film thickness of 50 nm was obtained on a PEN film substrate manufactured by Teijin PEI film substrate, except that a Sumitomo Metal Mine sputtering target prepared by using an atomic ratio of Sn to Zn of Sn/(Zn+Sn) of 0.28 was used. An oxide sputter film of Example 9 was obtained in the same manner as in Example 1 except for the sputtering film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Embodiment 10)
In Example 10, the atomic ratio Sn/(Zn+Sn) of Sn and Zn was 0.23, the atomic number Ta of Ta/(Zn+Sn+Ge+Ta) was 0.01, and the atomic ratio of Ge was Ge/(Zn). +Sn+Ge+Ta) was a Sputtered Metal Mine sputter target having a ratio of 0.04, and an oxide sputter film of 100 nm was obtained in the same manner as in Example 1. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Example 11)
In Example 11, except that the atomic ratio Sn/(Zn+Sn) of Sn and Zn was 0.23, the atomic number Ta of Ta and (Zn+Sn+Ge+Ta) was 0.01, and the atomic ratio of Ge was Ge/( A sputtering target having a ratio of 0.04 to Zn+Sn+Ge+ Ta) was prepared in the same manner as in Example 1 except that an oxide sputtering film having a film thickness of 50 nm was obtained on a PEN film substrate manufactured by Teijin, and the oxide of Example 11 was obtained. Coating. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Embodiment 12)
In Example 12, except that the atomic ratio Sn/(Zn+Sn) of Sn and Zn is 0.23, the atomic number Ta of Ta/(Zn+Sn+Ge+Ta) is 0.01, and the atomic ratio of Ge is Ge/( A sputtering target having a ratio of 0.04 to Zn+Sn+Ge+Ta) was prepared in the same manner as in Example 1 except that an oxide sputtering film having a film thickness of 10 nm was obtained on a PEN film substrate manufactured by Teijin, and the oxide of Example 12 was obtained. Coating. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Example 13)
In Example 13, except for the Sumitomo Metal Mine Sputtering Target prepared by using the ratio of the atomic ratio of Sn to Zn to Sn/(Zn+Sn) of 0.18, an oxide having a film thickness of 40 nm was obtained on a PEN film substrate manufactured by Teijin. An oxide sputter film of Example 13 was obtained in the same manner as in Example 1 except for the sputtering film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Example 14)
In Example 14, except for the Sumitomo Metal Mine Sputtering Target prepared by using the ratio of the atomic ratio of Sn to Zn to Sn/(Zn+Sn) of 0.28, an oxide having a film thickness of 40 nm was obtained on a PEN film substrate manufactured by Teijin. An oxide sputter film of Example 14 was obtained in the same manner as in Example 1 except for the sputtering film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Example 15)
In Example 15, except for the Sumitomo Metal Mine Sputtering Target prepared by using the ratio of the atomic ratio of Sn to Zn to Sn/(Zn+Sn) of 0.23, an oxide having a film thickness of 90 nm was obtained on a PEN film substrate manufactured by Teijin. An oxide sputter film of Example 15 was obtained in the same manner as in Example 1 except for the sputtering film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Embodiment 16)
In Example 16, a Sumitomo Metal Mine Sputtering Target prepared by using a ratio of Sn to Zn having an atomic ratio of Sn/(Zn+Sn) of 0.23 was used, and a film thickness of 100 nm was formed on a PEN film substrate manufactured by Teijin. An oxide sputter film of Example 16 was obtained in the same manner as in Example 1 except that an oxide sputtering film having a film thickness of 50 nm was obtained on the substrate of the SiO ₂ film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, and the oxygen permeability were confirmed.

(Example 17)
In Example 17, a Sumitomo Metal Mine sputter target prepared by using a ratio of Sn to Zn having an atomic ratio of Sn/(Zn+Sn) of 0.23 was used, and a film thickness of 100 nm was formed on a PEN film substrate manufactured by Teijin. An oxide sputter film of Example 17 was obtained in the same manner as in Example 1 except that an oxide sputtering film having a thickness of 50 nm was obtained on the substrate of the SiON film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, and the oxygen permeability were confirmed.

(Comparative Example 1)
In Comparative Example 1, an oxide sputter film was obtained in the same manner as in Example 1 except that a Sputtered Metal Mine Sputtering Target prepared by using a ratio of Sn to Zn of Sn/(Zn+Sn) of 0.15 was used. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Comparative Example 2)
In Comparative Example 2, an oxide of Comparative Example 2 was obtained in the same manner as in Example 1 except that a Sputtered Metal Mine Sputtering Target prepared by using a ratio of Sn to Zn of Sn/(Zn+Sn) of 0.30 was used. Sputtered film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Comparative Example 3)
In Comparative Example 3, an oxide of 5 nm thick was sputtered on a PEN film substrate manufactured by Teijin PEI film substrate, except that a Sumitomo Metal Mine sputter target having a ratio of Sn to Zn of Sn/(Zn+Sn) of 0.17 was used. An oxide sputter film of Comparative Example 3 was obtained in the same manner as in Example 1 except for the sputter film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

(Comparative Example 4)
In Comparative Example 4, a 5 nm-thick oxide film was sputtered on a PEN film substrate manufactured by Teijin PEN film substrate except that the Sumitomo Metal Mine sputtering target was prepared using a ratio of Sn to Zn atomic ratio Sn/(Zn+Sn) of 0.30. An oxide sputtered film of Comparative Example 4 was obtained in the same manner as in Example 1 except for the sputter film. In the same manner as in Example 1, the crystallinity, the water vapor transmission rate, the transmittance, and the oxygen permeability were confirmed.

The results of the above Examples 1 to 17 and Comparative Examples 1 to 4 are shown in Table 1.

As can be seen from Table 1, in all the examples in which Sn/(Zn+Sn) is set in the range of 0.18 or more and 0.29 or less, the water vapor transmission rate measured by the differential pressure method specified by the K7129 method of JIS standard is 50 to 100 nm. When it is 0.005 g/m ² /day or less, it is 0.009 g/m ² /day or less when it is less than 50 nm, and it is judged that it has favorable water vapor barrier property. Further, as is clear from Table 1, all the examples in which Sn/(Zn+Sn) is set in the range of 0.18 or more and 0.29 or less, the oxygen permeability measured by the differential pressure method specified by the K7126 method of JIS specification, When the film thickness of the coating film is 50 to 100 nm, it is 0.05 cc/m ² /day/atm or less, and when the film thickness of the oxide sputtering film is less than 50 nm, it is 0.09 cc/m ² /day/atm or less. Has good oxygen barrier properties. Therefore, in all of the examples, the water vapor barrier properties and the good oxygen barrier properties are all in the above range, and have good water vapor barrier properties and good oxygen barrier properties. Further, the transmittance measured at a wavelength of 550 nm was also 90% or more and had transparency. Further, a film thickness of an oxide sputter film of 100 nm or less which has the above-described performance and is more excellent in flexibility is obtained.

Further, a sputtering target prepared by using a ratio of Ta atom number Ta / (Zn + Sn + Ge + Ta) of 0.01 and a ratio of Ge atoms to Ge / (Zn + Sn + Ge + Ta) of 0.04 is used. Both the transmittance and the oxygen transmission rate showed good values.

On the other hand, in all the comparative examples in which Sn/(Zn+Sn) is outside the range of 0.18 or more and 0.29 or less, the water vapor transmission rate measured by the differential pressure method specified by the K7129 method of JIS standard is 50 to 100 nm. It is 0.005 g/m ² /day or more, and when it is less than 50 nm, it is 0.009 g/m ² /day or more, and does not have good water vapor barrier properties.

On the other hand, in all the comparative examples in which Sn/(Zn+Sn) is outside the range of 0.18 or more and 0.29 or less, the oxygen permeability measured by the differential pressure method specified by the K7126 method of JIS standard is obtained at 50 to 100 nm. 0.05 cc/m ² /day or more, when it is less than 50 nm, it is 0.09 cc/m ² /day or more, and does not have good oxygen barrier properties.

From the above, according to the present invention, it is possible to provide an oxide sputtering film having excellent transparency, good water vapor barrier properties or oxygen barrier properties, a method for producing an oxide sputtering film, and an oxide using a high-volume DC sputtering. Sintered body and transparent resin substrate.

[Industrial availability]

In the present invention, an oxide sputtering film having excellent transparency, good water vapor barrier properties or oxygen barrier properties, and oxidation are used, which employs high-performance DC sputtering with excellent water vapor barrier properties or oxygen barrier properties and flexibility. The method for producing a material sputtering film, the oxide sintered body, and the transparent conductive film substrate (such as a flexible display element) of the transparent resin substrate are extremely useful as components such as an OLED display element, a QD display element, and a QD sheet.

Further, although the embodiments and the embodiments of the present invention have been described in detail above, it is obvious that those skilled in the art can easily understand without departing from the novel aspects and effects of the present invention. Accordingly, such variations are all included within the scope of the invention.

For example, in the specification or the drawings, terms that are described at least once in a broader or synonymous but different term may be substituted for the different terms in any part of the specification or the drawings. Further, the configuration and operation of the oxide sputtering film, the oxide sputtering film, the oxide sintered body, and the transparent resin substrate are not limited to those described in the respective embodiments and examples of the present invention, and various changes can be implemented. .

Claims (10)

An oxide sputtered film characterized by an oxide sputter film containing amorphous and transparent Zn and Sn and having water vapor barrier properties or oxygen barrier properties, The ratio of the number of metal atoms of Zn to Sn is Sn/(Zn+Sn) of 0.18 or more and 0.29 or less. The oxide sputter film of claim 1, wherein the oxide sputtering film has a film thickness of 100 nm or less. The oxide sputter film of claim 1, wherein the oxide sputter film further contains Ta and Ge, The Ta/(Zn+Sn+Ge+Ta) ratio of the metal atomic ratio of Ta to Zn, Sn, and Ge is 0.01 or less. The ratio of the number of metal atoms of Ge to Zn, Sn, and Ta is Ge/(Zn+Sn+Ge+Ta) of 0.04 or less. The oxide sputter film of claim 1, wherein the water vapor transmission rate measured by the differential pressure method specified by the K7129 method of JIS is 0.005 g/ when the film thickness of the oxide sputter film is 50 to 100 nm. When m ² /day or less, when the film thickness of the oxide sputtering film is less than 50 nm, it is 0.009 g / m ² /day or less. The oxide sputter film of claim 1, wherein the oxygen permeability measured by the differential pressure method specified by the K7126 method of JIS is 0.05 cc/m ² when the film thickness of the oxide sputter film is 50 to 100 nm. /day/atm or less, when the film thickness of the oxide sputtering film is less than 50 nm, it is 0.09 cc/m ² /day/atm or less. An oxide sintered body characterized by a Sn-Zn-O-based oxide sintered body for use in an oxide sputtering film according to any one of claims 1 to 5, which is formed by a sputtering method. The ratio of the number of metal atoms of Zn and Sn contained in the oxide sintered body is Sn/(Zn+Sn) of 0.18 or more and 0.29 or less. The oxide sintered body of claim 6, wherein the oxide sintered body further contains Ta and Ge, The Ta/(Zn+Sn+Ge+Ta) ratio of the metal atomic ratio of Ta to Zn, Sn, and Ge is 0.01 or less. The ratio of the number of metal atoms of Ge to Zn, Sn, and Ta is Ge/(Zn+Sn+Ge+Ta) of 0.04 or less. A method for producing an oxide sputter film characterized by sputtering using a target made of an Sn-Zn-O oxide sintered body to obtain amorphous transparent Zn and Sn-containing water vapor barrier properties Or a film of oxygen barrier properties, The Sn/(Zn+Sn) ratio of the metal atomic ratio of Zn and Sn contained in the oxide sintered body used for the sputtering is 0.18 or more and 0.29 or less. The method for producing an oxide sputter film according to claim 8, wherein the oxide sputtering film has a film thickness of 100 nm or less. A transparent resin substrate characterized in that a transparent resin substrate comprising an amorphous oxide transparent film of Zn and Sn and having an oxide barrier property or an oxygen barrier property is formed on a transparent substrate. The oxide sputtering film is formed on at least one side of the substrate, The ratio of the number of metal atoms of Zn to Sn is Sn/(Zn+Sn) of 0.18 or more and 0.29 or less, and the film thickness of the oxide sputtering film is 100 nm or less.